JPH038446A - Preparation of catalyst for synthesizing dimethyl ether - Google Patents
Preparation of catalyst for synthesizing dimethyl etherInfo
- Publication number
- JPH038446A JPH038446A JP1143050A JP14305089A JPH038446A JP H038446 A JPH038446 A JP H038446A JP 1143050 A JP1143050 A JP 1143050A JP 14305089 A JP14305089 A JP 14305089A JP H038446 A JPH038446 A JP H038446A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- precipitate
- soln
- dimethyl ether
- contg
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title description 2
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 18
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000000977 initiatory effect Effects 0.000 abstract description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 3
- 235000017550 sodium carbonate Nutrition 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract 2
- 238000009413 insulation Methods 0.000 abstract 1
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- -1 dimethyl ethyl Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910017610 Cu(NO3) Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- BGGJELJUYBEGKP-UHFFFAOYSA-N chromium(2+);oxygen(2-) Chemical compound [O-2].[Cr+2] BGGJELJUYBEGKP-UHFFFAOYSA-N 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AIRCTMFFNKZQPN-UHFFFAOYSA-N oxidoaluminium Chemical compound [Al]=O AIRCTMFFNKZQPN-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は水素及び一酸化炭素よりジメチルエーテルを合
成する触媒の調製方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for preparing a catalyst for synthesizing dimethyl ether from hydrogen and carbon monoxide.
一般にＣＤ、Ｈ，等の合成ガスからガソリン留分を合成
するプロセスは未だ十分確立されたものでなく、多くの
問題点を有している。例えば、Ｆ−Ｔプロセスは生成物
の分布が広範囲であるため、ガソリンに適用する場合、
改質を行う必要があり、さらにＭＴＧプロセス（合成ガ
ス−メタノール−ガソリン）は、メタノール合成反応が
熱力学的平衡支配のためメタノール収率が低い等の問題
点を抱えている。一方、反応中間体としてジメチルエー
テルを経由する場合、メタノール合成に比べ熱力学的平
衡支配が緩和され、高収率でジメチルエーテルが得られ
ることが可能である。In general, the process of synthesizing gasoline fraction from synthesis gas such as CD, H, etc. has not yet been sufficiently established and has many problems. For example, the F-T process has a wide distribution of products, so when applied to gasoline,
In addition, the MTG process (synthesis gas-methanol-gasoline) has problems such as a low methanol yield because the methanol synthesis reaction is dominated by thermodynamic equilibrium. On the other hand, when dimethyl ether is used as a reaction intermediate, thermodynamic equilibrium control is relaxed compared to methanol synthesis, and dimethyl ether can be obtained in high yield.
これまで、メタノール合成触媒の開発研究は広く行われ
ており、酸化亜鉛一酸化クロム、酸化銅一酸化亜鉛等の
複合酸化物が用いられている。とりわけ近年酸化銅一酸
化亜鉛一酸化アルミニウムおよび／または酸化クロムの
三元又は四元組成物系触媒等が広く適用されている。Until now, development research on methanol synthesis catalysts has been widely conducted, and complex oxides such as zinc oxide, chromium monoxide, copper oxide and zinc monoxide have been used. In particular, catalysts based on ternary or quaternary compositions of copper oxide, zinc monoxide, aluminum monoxide and/or chromium oxide have been widely used in recent years.
ただし、ＣＤ、Ｌの合成ガスからジメチルエ−チル合成
用の触媒の調製方法に関する検討はあまりなされていな
く、通常のメタノール合成触媒とメタノール脱水触媒を
組み合わせて用いているが、ジメチルエーテルの収率は
低いままであり、触媒寿命も短い。However, there has not been much study on the method of preparing a catalyst for dimethyl ethyl synthesis from CD and L synthesis gas, and although a combination of an ordinary methanol synthesis catalyst and a methanol dehydration catalyst is used, the yield of dimethyl ether is low. The catalyst life is also short.
前記触媒が低活性で寿命が短い原因として副反応である
ジメチルエーテルの分解反応やＦ−Ｔ反応によるＣ析出
やワックス生成等によると考えられ、上記反応を抑制し
メタノール合成とメタノール脱水が逐次滴に高選択率で
生ずる触媒が望まれている。The reason for the low activity and short life of the catalyst is thought to be due to side reactions such as the decomposition reaction of dimethyl ether and the precipitation of C and wax formation due to the FT reaction. Catalysts that produce high selectivity are desired.
本発明は上記技術水準に鑑み、上記要望に答え得るジメ
チルエーテル合成用触媒の調製方法を提供しようとする
ものである。In view of the above-mentioned state of the art, the present invention aims to provide a method for preparing a catalyst for dimethyl ether synthesis that can meet the above-mentioned needs.
本発明は水素及び一酸化炭素からジメチルエーテルを合
成する触媒の調製方法において、所定温度に保温した沈
殿剤水溶液を攪拌しながらアルミニウムおよび／または
クロムと亜鉛を含んだ水溶液を沈殿剤水溶液に滴下して
沈殿物を生成させ、滴下後、銅を含んだ水溶液を滴下し
て沈殿物を生成させ、さらに熟成した沈殿物を洗浄、乾
燥後焼成することによって複合酸化物を得、この複合酸
化物とγ−アルミナを粉末混合することを特徴とするジ
メチルエーテル合成用触媒の調製方法である。The present invention is a method for preparing a catalyst for synthesizing dimethyl ether from hydrogen and carbon monoxide, in which an aqueous solution containing aluminum and/or chromium and zinc is dropped into an aqueous precipitant solution while stirring the aqueous precipitant solution kept at a predetermined temperature. A precipitate is generated, and after dropping, an aqueous solution containing copper is added dropwise to generate a precipitate, and the aged precipitate is washed, dried, and fired to obtain a composite oxide, and this composite oxide and γ - A method for preparing a catalyst for dimethyl ether synthesis, which comprises mixing alumina powder.
本発明において使用される沈殿剤水溶液はアルカリ水溶
液であり、通常０．０５Ｍ〜ＩＯＭの濃度のＮａｚＣＬ
、 ＮａＨＣＬＮａＯＨ、Ｋ２ＣＯ３ＮＨ，の水溶液
を用い、とりわけＮａ２ＣＯ３水溶液が好ましい。また
、銅、亜鉛、アルミニウムまたはクロムの画金属塩は硝
酸塩、塩化物、硫酸塩、酢酸塩を０．０１Ｍ〜１０Ｍの
濃度が用いられ、とりわけ硝酸塩が好ましい。さらに、
金属塩水溶液滴下時間は０．１分〜５時間で実施し、熟
成時間は０．１分〜３時間で行い、均一に沈殿物が生成
される必要がある。また沈殿及び熟成温度は１５〜９５
℃の範囲内において実施するのがよい。得られた沈殿物
はＮ［１，−やＮａ＋等のイオンを十分洗浄した後、１
８０〜４００℃の範囲の温度で乾燥して複合酸化物を得
るようにするのがよい。この複合酸化物の組成は原子比
でＣｕ：１００に対してＺｎ： １０〜２５０．＾ｌ及
び／またはＣｒ：１〜１００の範囲になるようにするの
がよい。The precipitant aqueous solution used in the present invention is an alkaline aqueous solution, and usually contains NazCL at a concentration of 0.05M to IOM.
, NaHCLNaOH, K2CO3NH, an aqueous solution of Na2CO3 is particularly preferred. Further, as the picture metal salt of copper, zinc, aluminum or chromium, nitrate, chloride, sulfate or acetate is used at a concentration of 0.01M to 10M, with nitrate being particularly preferred. moreover,
The dropping time of the aqueous metal salt solution should be 0.1 minutes to 5 hours, and the aging time should be 0.1 minutes to 3 hours, so that a precipitate is uniformly produced. Also, the precipitation and aging temperature is 15 to 95
It is preferable to carry out the test within the range of ℃. The obtained precipitate was thoroughly washed with ions such as N[1,- and Na+, and then
It is preferable to obtain a composite oxide by drying at a temperature in the range of 80 to 400°C. The composition of this composite oxide is Cu: 100 to Zn: 10-250. ^l and/or Cr: preferably in the range of 1 to 100.
この複合酸化物とｒ−Ａｌｉａｓを６０〜１００メツシ
ユに粉砕して粉末混合物とした後、１６〜２８メツシユ
に整粒し、ジメチルエーテル合成用触媒に供するのであ
るが、複合酸化物とＴ−Ａ１２０３の混合比は重量％で
９５：５〜２０：８０、好ましくは７０：３０〜５０：
５０である。この複合酸化物はＣｕＯ、ＺｎＯの結晶種
が認められるが、はとんどアモルファスであり、ＣＤ吸
着活性点である銅が高分散に分布しているため、ジメチ
ルエーテル合成の際に生ずる副反応（Ｆ−Ｔ反応、分解
反応）を抑制し、長寿命な触媒となる。This composite oxide and r-Alias are ground into a powder mixture of 60 to 100 meshes, then sized to 16 to 28 meshes, and used as a catalyst for dimethyl ether synthesis. The mixing ratio is 95:5 to 20:80 by weight, preferably 70:30 to 50:
It is 50. Although crystal seeds of CuO and ZnO are observed in this composite oxide, it is mostly amorphous, and copper, which is an active site for CD adsorption, is highly dispersed, so side reactions ( FT reaction, decomposition reaction), resulting in a long-life catalyst.
以下、実施例により、ジメチルエーテル合成用触媒の調
製方法を詳述する。Hereinafter, a method for preparing a catalyst for dimethyl ether synthesis will be described in detail with reference to Examples.
〔実施例１〕
炭酸ナトリウム（Ｎａ２ＣＬ ２．５ ｍｇ）を水２
１に溶かし６０℃で保温する。このアルカリ水溶液を溶
液Ａとする。硝酸亜鉛［Ｚｎ（Ｎｏ、）２６Ｈ，０：０
、２２５ｍｏｌ ）と硝酸アルミニウム（、Ａ１（ＮＯ
，）。[Example 1] Sodium carbonate (Na2CL 2.5 mg) was added to water 2
1 and keep warm at 60℃. This alkaline aqueous solution will be referred to as solution A. Zinc nitrate [Zn(No,)26H, 0:0
, 225 mol) and aluminum nitrate (, A1(NO
,).
・９Ｈ２０： ０．０７５ ｍｏｌ ］を水４００ ｃ
ｃに溶かし、８０℃に保温し、この酸性溶液を溶液Ｂと
する。・9H20: 0.075 mol] in 400 c of water
This acidic solution is called solution B.
硝酸銅［Ｃｕ（ＮＬ）２・３Ｈ，Ｏ： ０．３ ｍｏｌ
］を水２００ｃｃに溶かし６０℃に保温し、この酸性
溶液を溶液Ｃとする。Copper nitrate [Cu(NL)2.3H,O: 0.3 mol
] was dissolved in 200 cc of water and kept at 60°C, and this acidic solution was designated as solution C.
まず、攪拌しながら溶液へに溶液Ｂを２０分にわたって
均一に滴下し懸濁液を得る。溶液Ｂを滴下後、次に溶液
Ｃを前記懸濁液に３０分にわたって一定速度で滴下し沈
殿物を得る。滴下終了時のｐＨは８であった。First, solution B is uniformly added dropwise to the solution over 20 minutes while stirring to obtain a suspension. After adding Solution B dropwise, Solution C is then added dropwise to the suspension at a constant rate over 30 minutes to obtain a precipitate. The pH at the end of the dropwise addition was 8.
滴下後１時間の熟成を行い、次に、沈殿物のろ過および
Ｎａイオン、ＮＯ，イオンが検知されないよう洗浄する
。さらに、１００℃、２４時間乾燥し、その後３００℃
、３時間焼成することによりＣｕＯＺｎ０−ＡＩｚＯｓ
の複合酸化物を得る。この複合酸化物とｒ−Ａｌ２Ｏ３
を６０〜１００メツシユに粉砕し、７０：３０（ｗｔ％
）の混合比で粉末混合した後１６〜２８メツシユに整粒
し、ジメチルエーテル合成用触媒を得た。この触媒を触
媒１とする。After dropping, the mixture is aged for 1 hour, and then the precipitate is filtered and washed so that Na ions, NO, and ions are not detected. Further, dry at 100°C for 24 hours, then at 300°C.
, CuOZn0-AIzOs by firing for 3 hours
Obtain a composite oxide of This composite oxide and r-Al2O3
was crushed into 60 to 100 meshes and 70:30 (wt%
) The powders were mixed at a mixing ratio of 16 to 28 mesh, and a catalyst for dimethyl ether synthesis was obtained. This catalyst will be referred to as catalyst 1.
〔実施例２〕
上記のＢ液として硝酸亜鉛［Ｚｎ（ＮＬ）ｚ ’ ６Ｈ
−０：］０．２５＋ｎｏｌ、硝酸アルミニウム［：ＡＩ
（ＮＯａ）＋・９Ｈ＝０ ］ ０．１ ｍｏｌを水に添
加する以外は実施例１と同様の調製方法にてジメチルエ
ーテル合成触媒を調製した。この触媒を触媒２とする。[Example 2] Zinc nitrate [Zn(NL)z' 6H
-0:]0.25+nol, aluminum nitrate [:AI
A dimethyl ether synthesis catalyst was prepared in the same manner as in Example 1 except that 0.1 mol of (NOa)+·9H=0] was added to water. This catalyst will be referred to as catalyst 2.
さらにＢ液の硝酸亜鉛ＣＺｎ （ＮＯ３） ２ ” ６
Ｈ２０］の量を０．３ｍｏｌとし、かつＣ液の硝酸銅［
Ｃｕ（ＮＯ３）ｚ・３）１．０１を０．３２５ｍｏｌに
する以外は実施例１と同様に調製して触媒３を、またＢ
液の硝酸アルミニウム［Ａｌ （Ｎｏ３） ３・９ Ｈ
２Ｏ〕の量を０．０５ｍｏｌとし、かつＣ液の硝酸銅［
Ｃｕ（ＮＯ３）２・３）＋２０］を０．２５ｍｏｌにす
る以外は実施例１と同様に調製して触媒４を得た。Furthermore, zinc nitrate CZn (NO3) 2 ” 6 of B solution
The amount of copper nitrate [H20] was 0.3 mol, and the amount of copper nitrate [
Catalyst 3 and B
Liquid aluminum nitrate [Al (No3) 3.9 H
2O] is 0.05 mol, and the amount of copper nitrate [
Catalyst 4 was obtained in the same manner as in Example 1 except that Cu(NO3)2.3)+20] was changed to 0.25 mol.
〔実施例３〕
Ｂ液に硝酸亜鉛ＣＺｎ（ＮＯ＊）＊ ・６Ｈ２０］ ０
．２５ ｍｏｌと硝酸クロム［Ｃｒ（ＮＯｓ）ｓ ・９
Ｈ２Ｏ］を０．１ｍｏ！添加し、それ以外は実施例１
と同様の調製方法によって調製して触媒５を得た。[Example 3] Zinc nitrate CZn (NO*)* ・6H20] 0 in B solution
．． 25 mol and chromium nitrate [Cr(NOs)s 9
H2O] 0.1 mo! Added, otherwise Example 1
Catalyst 5 was obtained by the same method as above.
さらにＢ液を硝酸亜鉛ＣＺｎ（Ｎｏ、） ２ ・６ｔ１
２ｏ］を０、２７５ｍｏ！ 、硝酸クロム［Ｃｒ（ＮＯ
３）３・９ Ｈ２Ｏ〕を０．０５ｍｏｌ、硝酸アルミニ
ウム〔ＡＩ （ＮＯ３） ３・９ Ｈ２Ｏ］ ０．０５
ｍｏｌ添加し、それ以外は実施例１と同様の調製方法に
よって調製して触媒６を得た。Further, add B solution to zinc nitrate CZn (No,) 2 ・6t1
2o] to 0, 275mo! , chromium nitrate [Cr(NO
3) 0.05 mol of 3・9 H2O], 0.05 mol of aluminum nitrate [AI (NO3) 3・9 H2O]
Catalyst 6 was obtained using the same method as in Example 1 except that mol was added.
〔実施例４〕
実施例１と同様の方法により調製した複合酸化物とｒ−
Ａｌ２Ｏ３を６０：４０，５０：５０（重量比）の混合
比にて粉末混合した後１６〜２８メツシユに整粒して触
媒７、触媒８を得た。[Example 4] Composite oxide prepared by the same method as Example 1 and r-
After powder-mixing Al2O3 at a mixing ratio of 60:40 and 50:50 (weight ratio), catalysts 7 and 8 were obtained by sizing into 16 to 28 meshes.
〔比較例１〕
実施例１と同様の組成の溶液Ａ、Ｂ、Ｃを用いて、下記
の方法により従来触媒を調製した。[Comparative Example 1] Using solutions A, B, and C having the same composition as in Example 1, a conventional catalyst was prepared by the following method.
まず、溶液Ｂに溶液Ｃを一度に加え亜鉛、アルミニウム
、銅イオンを有する酸性水溶液（ｐＨ＝３）を得る。こ
の水溶液に溶液Ａを攪拌しながら一定速度で３０分間に
わたり滴下する。滴下終了時のｐＨは８であった。滴下
後２時間の熟成を行い、その後実施例１と同様の調製方
法にて複合酸化物を得、さらにγ−Ａ１２０３と７０：
３０ （重量比）にて粉末混合することにより触媒９を
得た。First, solution C is added to solution B at once to obtain an acidic aqueous solution (pH=3) containing zinc, aluminum, and copper ions. Solution A is added dropwise to this aqueous solution at a constant rate for 30 minutes while stirring. The pH at the end of the dropwise addition was 8. Aging was performed for 2 hours after dropping, and then a composite oxide was obtained by the same preparation method as in Example 1, and further γ-A1203 and 70:
Catalyst 9 was obtained by powder mixing at a weight ratio of 30%.
実施例１〜３、比較例１にて得られた触媒１〜９のメタ
ノール合成反応の活性評価試験を下記の条件にて行った
。An activity evaluation test for the methanol synthesis reaction of catalysts 1 to 9 obtained in Examples 1 to 3 and Comparative Example 1 was conducted under the following conditions.
原料ガス： Ｌ ６７ｍｏ１％、 Ｃｏ ３３ｍｏ１
％ＧＨ３Ｖ：８０００ｈ−’
反応温度：２５０℃
反応圧カニ ５０ ｋｇ／ｃＪＧ
触媒は２ ｃｃをマイクロリアクターに充填し、８２３
％／Ｎ、ペースガスで還元処理した後、原料ガスを供給
し、初期活性評価を行った。各触媒の初期活性評価結果
を表１に示す。Raw material gas: L 67mo1%, Co 33mo1
%GH3V: 8000 h-' Reaction temperature: 250°C Reaction pressure 50 kg/cJG 2 cc of catalyst was packed into a microreactor, and 823
%/N, and after reduction treatment with pace gas, raw material gas was supplied and initial activity evaluation was performed. Table 1 shows the initial activity evaluation results for each catalyst.
上記結果より、本発明より得られた触媒１〜８は触媒９
に比べ初期ＣＤ転化率が高いことがわかる。From the above results, catalysts 1 to 8 obtained according to the present invention are different from catalyst 9.
It can be seen that the initial CD conversion rate is higher than that of the sample.
初期活性評価に供した触媒１、触媒９を耐久性試験用触
媒に供した。反応条件は実施例５と同様である。活性評
価を表２に示す。Catalyst 1 and Catalyst 9, which were used for initial activity evaluation, were used as catalysts for durability testing. The reaction conditions are the same as in Example 5. Activity evaluation is shown in Table 2.
表２
表２に示すように本発明で調製したジメチルエーテル合
成触媒は従来触媒に比べて大幅に耐久部に優れているこ
とが判明した。Table 2 As shown in Table 2, the dimethyl ether synthesis catalyst prepared according to the present invention was found to be significantly superior in durability compared to conventional catalysts.
本発明により、水素と一酸化炭素より、初期活性が高く
、高寿命のジメチルエーテル合成用触媒が得られる。According to the present invention, a catalyst for dimethyl ether synthesis having higher initial activity and longer life than hydrogen and carbon monoxide can be obtained.
Claims (1)
る触媒の調製方法において、所定温度に保温した沈殿剤
水溶液を攪拌しながらアルミニウムおよび／またはクロ
ムと亜鉛を含んだ水溶液を沈殿剤水溶液に滴下して沈殿
物を生成させ、滴下後、銅を含んだ水溶液を滴下して沈
殿物を生成させ、さらに熟成した沈殿物を洗浄、乾燥後
焼成することによって複合酸化物を得、この複合酸化物
とγ−アルミナを粉末混合することを特徴とするジメチ
ルエーテル合成用触媒の調製方法。1. In a method for preparing a catalyst for synthesizing dimethyl ether from hydrogen and carbon monoxide, an aqueous solution containing aluminum and/or chromium and zinc is dropped into an aqueous precipitant solution while stirring the aqueous precipitant solution kept at a predetermined temperature to cause precipitation. After dropping, an aqueous solution containing copper is added dropwise to form a precipitate, and the aged precipitate is washed, dried and fired to obtain a composite oxide, and this composite oxide and γ- A method for preparing a catalyst for dimethyl ether synthesis, which comprises mixing alumina powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1143050A JPH038446A (en) | 1989-06-07 | 1989-06-07 | Preparation of catalyst for synthesizing dimethyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1143050A JPH038446A (en) | 1989-06-07 | 1989-06-07 | Preparation of catalyst for synthesizing dimethyl ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH038446A true JPH038446A (en) | 1991-01-16 |
Family
ID=15329747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1143050A Pending JPH038446A (en) | 1989-06-07 | 1989-06-07 | Preparation of catalyst for synthesizing dimethyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH038446A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5753716A (en) * | 1997-02-21 | 1998-05-19 | Air Products And Chemicals, Inc. | Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process |
| JP2006225615A (en) * | 2005-02-21 | 2006-08-31 | Mitsubishi Heavy Ind Ltd | Method for producing desulfurization agent for hydrocarbonaceous fuel and desulfurization agent for hydrocarbonaceous fuel |
| KR100863491B1 (en) * | 2007-05-01 | 2008-10-15 | 한국과학기술원 | Hybrid catalysts for dme steam reforming to produce hydrogen as fuel cell feed, and application to producing hydrogen and the method thereof |
-
1989
- 1989-06-07 JP JP1143050A patent/JPH038446A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5753716A (en) * | 1997-02-21 | 1998-05-19 | Air Products And Chemicals, Inc. | Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process |
| JP2006225615A (en) * | 2005-02-21 | 2006-08-31 | Mitsubishi Heavy Ind Ltd | Method for producing desulfurization agent for hydrocarbonaceous fuel and desulfurization agent for hydrocarbonaceous fuel |
| KR100863491B1 (en) * | 2007-05-01 | 2008-10-15 | 한국과학기술원 | Hybrid catalysts for dme steam reforming to produce hydrogen as fuel cell feed, and application to producing hydrogen and the method thereof |
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