JP6611390B1 - Methacrylic acid production equipment - Google Patents

Methacrylic acid production equipment Download PDF

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JP6611390B1
JP6611390B1 JP2018213843A JP2018213843A JP6611390B1 JP 6611390 B1 JP6611390 B1 JP 6611390B1 JP 2018213843 A JP2018213843 A JP 2018213843A JP 2018213843 A JP2018213843 A JP 2018213843A JP 6611390 B1 JP6611390 B1 JP 6611390B1
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JP2020079221A (en
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正二 犬飼
正二 犬飼
範明 須安
範明 須安
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0046Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053Details of the reactor
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    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/38Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00Compounds having —CHO groups
    • C07C47/20Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/21Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C47/22Acryaldehyde; Methacryaldehyde
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03Monocarboxylic acids
    • C07C57/04Acrylic acid; Methacrylic acid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00164Controlling or regulating processes controlling the flow
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277Apparatus
    • B01J2219/00279Features relating to reactor vessels
    • B01J2219/00331Details of the reactor vessels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277Apparatus
    • B01J2219/00351Means for dispensing and evacuation of reagents

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Abstract

【課題】設備を簡略化し得るメタクリル酸の製造装置を提供すること。【解決手段】第一反応器10と、第二反応器R1〜Rn(nは2以上の整数を示す)と、第一反応器10の出口及び第二反応器R1〜Rnの入口に接続され、第一反応器10の出口から出た流を分岐して第二反応器R1〜Rnのそれぞれの入口に供給するラインLAと、第二反応器R1〜Rnのそれぞれの出口に接続され、第二反応器R1〜Rnの出口から出た流を合流させるラインLBと、を備え、第二反応器R1〜Rn底部の高さA、第二反応器R1〜Rnそれぞれの高さH、ラインLAの分岐部から第二反応器R1〜Rnの入口までの流路における配管、及び第二反応器R1〜Rnの出口からラインLBの合流部までの流路における配管が、所定の条件を満たす、メタクリル酸の製造装置。【選択図】図1An apparatus for producing methacrylic acid capable of simplifying equipment is provided. The first reactor 10 is connected to the second reactors R1 to Rn (n is an integer of 2 or more), the outlet of the first reactor 10 and the inlets of the second reactors R1 to Rn. A line LA branched from the outlet of the first reactor 10 and supplied to the respective inlets of the second reactors R1 to Rn and connected to the respective outlets of the second reactors R1 to Rn, A line LB for joining the flows from the outlets of the two reactors R1 to Rn, the height A of the bottom of the second reactors R1 to Rn, the height H of each of the second reactors R1 to Rn, the line LA The pipe in the flow path from the branch part of the second reactor R1 to Rn and the pipe in the flow path from the outlet of the second reactor R1 to Rn to the merge part of the line LB satisfy a predetermined condition, Equipment for producing methacrylic acid. [Selection] Figure 1

Description

本発明は、メタクリル酸の製造装置に関する。   The present invention relates to an apparatus for producing methacrylic acid.

特許文献1には、メタクリル酸を製造するための方法が記載されている。   Patent Document 1 describes a method for producing methacrylic acid.

国際公開第2008/145417号International Publication No. 2008/145417

メタクリル酸の製造に用いられる製造装置は、設備が簡便であることが好ましい。そこで、本発明は、設備を簡略化し得るメタクリル酸の製造装置を提供することを目的とする。   The production apparatus used for producing methacrylic acid preferably has simple facilities. Then, an object of this invention is to provide the manufacturing apparatus of methacrylic acid which can simplify an installation.

本発明のメタクリル酸の製造装置は、イソブチレン及び/又はtert−ブチルアルコール(以下、「TBA」と記載する)と酸素とからメタクロレインを得る第一反応器と、メタクロレイン及び酸素を反応させてメタクリル酸を得る複数の第二反応器R〜R(nは2以上の整数を示す)と、第一反応器の出口及び第二反応器R〜Rの入口に接続され、第一反応器の出口から出た流を分岐して第二反応器R〜Rのそれぞれの入口に供給するラインLAと、第二反応器R〜Rのそれぞれの出口に接続され、第二反応器R〜Rの出口から出た流を合流させるラインLBと、を備え、第二反応器R〜Rそれぞれの底部の高さA〜Aが式(2)を満たすように、第二反応器R〜Rが設置され、第二反応器R〜Rそれぞれの高さH〜Hが式(3)を満たし、ラインLAの分岐部から第二反応器R〜Rの入口R1i〜Rniまでのそれぞれの流路C1i〜Cniにおける配管の内径D1i〜Dni及び長さL1i〜Lniが式(4a)及び式(4b)の条件を満たし、第二反応器R〜Rの出口R1j〜RnjからラインLBの合流部までのそれぞれの流路C1j〜Cnjにおける配管の内径D1j〜Dnj及び長さL1j〜Lnjが式(5a)及び式(5b)の条件を満たす。
(Amax−Amin)/Aave≦0.02 ・・・(2)
[Amaxは、A〜Aのうちの最大値を示し、Aminは、A〜Aのうちの最小値を示し、Aaveは、A〜Aの平均値を示す。]
(Hmax−Hmin)/Have≦0.02 ・・・(3)
[Hmaxは、H〜Hのうちの最大値を示し、Hminは、H〜Hのうちの最小値を示し、Haveは、H〜Hの平均値を示す。]
(Dmax(i)/Dmin(i))≦1.025 ・・・(4a)
[Dmax(i)は、D1i〜Dniのうちの最大値を示し、Dmin(i)は、D1i〜Dniのうちの最小値を示す。]
(Lmax(i)/Lmin(i))≦1.05 ・・・(4b)
[Lmax(i)は、L1i〜Lniのうちの最大値を示し、Lmin(i)は、L1i〜Lniのうちの最小値を示す。]
(Dmax(j)/Dmin(j))≦1.025 ・・・(5a)
[Dmax(j)は、D1j〜Dnjのうちの最大値を示し、Dmin(j)は、D1j〜Dnjのうちの最小値を示す。]
(Lmax(j)/Lmin(j))≦1.05 ・・・(5b)
[Lmax(j)は、L1j〜Lnjのうちの最大値を示し、Lmin(j)は、L1j〜Lnjのうちの最小値を示す。]
The apparatus for producing methacrylic acid of the present invention comprises a first reactor for obtaining methacrolein from isobutylene and / or tert-butyl alcohol (hereinafter referred to as “TBA”) and oxygen, and reacting methacrolein and oxygen. A plurality of second reactors R 1 to R n for obtaining methacrylic acid (n represents an integer of 2 or more), an outlet of the first reactor and an inlet of the second reactors R 1 to R n , each and line LA to be supplied to the inlet of the second reactor R 1 to R n branches the flow exiting from the outlet of the first reactor is connected to a respective outlet of the second reactor R 1 to R n, a line LB which joins the flow exiting from the outlet of the second reactor R 1 to R n, comprises a second reactor R 1 to R n height a 1 to a n of each bottom equation (2) The second reactors R 1 to R n are installed so as to satisfy Reactor R 1 to R n respective heights H 1 to H n satisfies Equation (3), each of the branches of the line LA to the inlet R 1i to R ni of the second reactor R 1 to R n The inner diameters D 1i to D ni and the lengths L 1i to L ni of the pipes in the flow paths C1i to Cni satisfy the conditions of the expressions (4a) and (4b), and the outlets R 1j of the second reactors R 1 to R n The inner diameters D 1j to D nj and the lengths L 1j to L nj of the pipes in the respective flow paths C1j to Cnj from ˜R nj to the joining part of the line LB satisfy the conditions of the expressions (5a) and (5b).
(A max −A min ) / A ave ≦ 0.02 (2)
[A max represents the maximum value of A 1 ~A n, A min denotes the minimum value of A 1 ~A n, A ave represents the average value of A 1 to A n. ]
(H max −H min ) / H ave ≦ 0.02 (3)
[H max represents the maximum value of H 1 ~H n, H min represents the minimum value of the H 1 ~H n, H ave represents the average value of H 1 to H n. ]
(D max (i) / D min (i) ) ≦ 1.025 (4a)
[D max (i) indicates the maximum value of D 1i to D ni , and D min (i) indicates the minimum value of D 1i to D ni . ]
(L max (i) / L min (i) ) ≦ 1.05 (4b)
[L max (i) indicates the maximum value of L 1i to L ni , and L min (i) indicates the minimum value of L 1i to L ni . ]
(D max (j) / D min (j) ) ≦ 1.025 (5a)
[D max (j) indicates the maximum value of D 1j to D nj , and D min (j) indicates the minimum value of D 1j to D nj . ]
(L max (j) / L min (j) ) ≦ 1.05 (5b)
[L max (j) represents the maximum value among L 1j to L nj , and L min (j) represents the minimum value among L 1j to L nj . ]

このようなメタクリル酸の製造装置によれば、設備を簡略化し得る。   According to such an apparatus for producing methacrylic acid, the equipment can be simplified.

上記メタクリル酸の製造装置においては、流路C1i〜Cniに、同じ流量で同じ流体を通過させたときに、各流路C1i〜Cniにおける入口と出口との間の圧力損失ΔP1i〜ΔPniが、式(1a)を満たし、流路C1j〜Cnjに、同じ流量で同じ流体を通過させたときに、各流路C1j〜Cnjにおける入口と出口との間の圧力損失ΔP1j〜ΔPnjが、式(1b)を満たすことが好ましい。
(ΔPmax(i)−ΔPmin(i))/ΔPave(i)≦0.10 ・・・(1a)
[ΔPmax(i)は、ΔP1i〜ΔPniのうちの最大値を示し、ΔPmin(i)は、ΔP1i〜ΔPniのうちの最小値を示し、ΔPave(i)は、ΔP1i〜ΔPniの平均値を示す。]
(ΔPmax(j)−ΔPmin(j))/ΔPave(j)≦0.10 ・・・(1b)
[ΔPmax(j)は、ΔP1j〜ΔPnjのうちの最大値を示し、ΔPmin(j)は、ΔP1j〜ΔPnjのうちの最小値を示し、ΔPave(j)は、ΔP1j〜ΔPnjの平均値を示す。]
In the methacrylic acid production apparatus, when the same fluid is passed through the flow paths C1i to Cni at the same flow rate, the pressure loss ΔP 1i to ΔP ni between the inlet and the outlet in each of the flow paths C1i to Cni is When the same fluid is passed through the flow paths C1j to Cnj at the same flow rate, the pressure loss ΔP 1j to ΔP nj between the inlet and the outlet in each flow path C1j to Cnj is It is preferable to satisfy the formula (1b).
(ΔP max (i) −ΔP min (i) ) / ΔP ave (i) ≦ 0.10 (1a)
[ΔP max (i) represents the maximum value among ΔP 1i to ΔP ni , ΔP min (i) represents the minimum value among ΔP 1i to ΔP ni , and ΔP ave (i) represents ΔP 1i The average value of ~ ΔP ni is shown. ]
(ΔP max (j) −ΔP min (j) ) / ΔP ave (j) ≦ 0.10 (1b)
[ΔP max (j) represents the maximum value among ΔP 1j to ΔP nj , ΔP min (j) represents the minimum value among ΔP 1j to ΔP nj , and ΔP ave (j) represents ΔP 1j The average value of ~ ΔP nj is shown. ]

これにより、設備を更に簡略化し得る。   Thereby, an installation can be further simplified.

本発明によれば、設備を簡略化し得るメタクリル酸の製造装置が提供される。   ADVANTAGE OF THE INVENTION According to this invention, the manufacturing apparatus of methacrylic acid which can simplify an installation is provided.

本実施形態のメタクリル酸の製造装置の一例を示す図である。It is a figure which shows an example of the manufacturing apparatus of methacrylic acid of this embodiment.

本明細書において、イソブチレンとは2−メチルプロペンを指す。   As used herein, isobutylene refers to 2-methylpropene.

まず、図1を参照して、本実施形態に係るメタクリル酸の製造装置100について説明する。図1は、本実施形態のメタクリル酸の製造装置の一例を示す図である。   First, a methacrylic acid production apparatus 100 according to this embodiment will be described with reference to FIG. FIG. 1 is a diagram illustrating an example of a methacrylic acid production apparatus according to the present embodiment.

この製造装置100は、第二反応器が2つの反応器からなる場合の製造装置の一例である。すなわち、製造装置100は、複数の第二反応器R〜R(nは2以上の整数を示す)において、nが2である場合の一態様を示す。製造装置100の説明において、「A〜A」、「H〜H」、「D1i〜Dni」、「L1i〜Lni」、「「D1j〜Dnj」、「L1j〜Lnj」、「ΔP1i〜ΔPni」及び「ΔP1j〜ΔPnj」との記載は、それぞれ「A及びA」、「H及びH」、「D1i及びD2i」、「L1i及びL2i」、「D1j及びD2j」、「L1j及びL2j」、「ΔP1i及びΔP2i」並びに「ΔP1j及びΔP2j」を意味する。 This manufacturing apparatus 100 is an example of a manufacturing apparatus in the case where the second reactor includes two reactors. That is, the manufacturing apparatus 100 shows an aspect in which n is 2 in a plurality of second reactors R 1 to R n (n represents an integer of 2 or more). In the description of the manufacturing apparatus 100, “A 1 to An ”, “H 1 to H n ”, “D 1i to D ni ”, “L 1i to L ni ”, ““ D 1j to D nj ”,“ L “ 1j to L nj ”, “ΔP 1i to ΔP ni ”, and “ΔP 1j to ΔP nj ” are referred to as “A 1 and A 2 ”, “H 1 and H 2 ”, “D 1i and D 2i ”, respectively. , “L 1i and L 2i ”, “D 1j and D 2j ”, “L 1j and L 2j ”, “ΔP 1i and ΔP 2i ” and “ΔP 1j and ΔP 2j ”.

製造装置100は、第一反応器10、第二反応器20、分離手段60、並びにラインLA及びLBを主として備える。ラインLAはガスミキサー50bを備える。第二反応器20は反応器R及びRからなる。 The production apparatus 100 mainly includes a first reactor 10, a second reactor 20, a separation means 60, and lines LA and LB. The line LA includes a gas mixer 50b. Second reactor 20 comprises a reaction vessel R 1 and R 2.

第一反応器10の入口10iには、イソブチレン及び/又はTBAと酸素とを含むガスの供給源(S0)がラインL10を介して接続されている。   A gas supply source (S0) containing isobutylene and / or TBA and oxygen is connected to the inlet 10i of the first reactor 10 via a line L10.

第一反応器10は、イソブチレン及び/又はTBAと酸素とからメタクロレインを得る反応器である。   The first reactor 10 is a reactor for obtaining methacrolein from isobutylene and / or TBA and oxygen.

第一反応器10は、容器内に触媒が充填された反応器であることが好適である。第一反応器10は、容器内に触媒を充填した固定床反応装置であることができる。流の向きに制限はなく、アップフローでもダウンフローでもよい。イソブチレン及び/又はTBAと酸素とからメタクロレインを合成する反応に用いられる触媒の例は、モリブデン及びビスマスを含む金属酸化物である。   The first reactor 10 is preferably a reactor in which a container is filled with a catalyst. The first reactor 10 can be a fixed bed reactor filled with a catalyst in a vessel. There is no restriction on the direction of flow, and it may be upflow or downflow. An example of a catalyst used in a reaction for synthesizing methacrolein from isobutylene and / or TBA and oxygen is a metal oxide containing molybdenum and bismuth.

イソブチレンと酸素とからメタクロレインを得る場合、イソブチレンと酸素とが反応して、これによりメタクロレインが生成する。イソブチレンに代えてTBAを用いることも可能である。TBAと酸素とからメタクロレインを得る場合、TBAの脱水反応によりイソブチレンが生成し、生成したイソブチレンと酸素とが反応してメタクロレインが生成するものと考えられる。イソブチレンに代えてTBAを用いることができる理由は、第一反応器10内では、イソブチレンの酸化反応が律速となることにあると考えられる。イソブチレンとTBAとは、併用することもできる。   When obtaining methacrolein from isobutylene and oxygen, isobutylene and oxygen react to produce methacrolein. It is also possible to use TBA instead of isobutylene. When obtaining methacrolein from TBA and oxygen, it is considered that isobutylene is produced by the dehydration reaction of TBA, and the produced isobutylene and oxygen react to produce methacrolein. The reason why TBA can be used in place of isobutylene is considered to be that the oxidation reaction of isobutylene becomes rate limiting in the first reactor 10. Isobutylene and TBA can be used in combination.

第一反応器10の出口10jと第二反応器20の入口R1i及びR2iとが、ラインLAにより接続されている。第二反応器20の入口R1i及びR2iは、それぞれ反応器R及びRの入口である。ラインLAは、第一反応器10の出口10jから出た流を分岐して反応器R及びRのそれぞれの入口に供給するラインである。 The outlet 10j of the first reactor 10 and the inlets R 1i and R 2i of the second reactor 20 are connected by a line LA. The inlets R 1i and R 2i of the second reactor 20 are the inlets of the reactors R 1 and R 2 , respectively. Line LA is a line for supplying the respective inlets of the branching flow exiting from the outlet 10j reactor R 1 and R 2 of the first reactor 10.

ラインLAのガスミキサー50bの入口50bには、ラインL22が接続されている。ラインL22は、ラインLAと酸素供給源(S1)とを接続するラインであり、ラインの一部にコンプレッサー55が設けられている。 The inlet 50b m of gas mixer 50b of the line LA, line L22 is connected. The line L22 is a line connecting the line LA and the oxygen supply source (S1), and a compressor 55 is provided in a part of the line.

第二反応器20は、メタクロレイン及び酸素を反応させてメタクリル酸を得る反応器である。第二反応器20を構成する反応器は、容器内に触媒が充填された反応器であることが好適である。第二反応器20を構成する反応器は、容器内に触媒を充填した固定床反応装置であることができる。固定床反応装置は、例えば、触媒粒子と必要に応じ不活性粒子とを含む固体粒子を、多管式熱交換器の各チューブに充填した装置であってもよい。流の向に特に限定はなく、アップフローでもダウンフローでもよい。メタクロレイン及び酸素からメタクリル酸を合成する反応に用いられる触媒の例は、リン及びモリブデンを含むヘテロポリ酸化合物である。   The second reactor 20 is a reactor for obtaining methacrylic acid by reacting methacrolein and oxygen. The reactor constituting the second reactor 20 is preferably a reactor filled with a catalyst in a container. The reactor constituting the second reactor 20 can be a fixed bed reactor in which a vessel is filled with a catalyst. The fixed bed reaction apparatus may be, for example, an apparatus in which solid tubes containing catalyst particles and, if necessary, inert particles are filled in each tube of a multitubular heat exchanger. There is no particular limitation on the direction of flow, and it may be upflow or downflow. An example of the catalyst used in the reaction for synthesizing methacrylic acid from methacrolein and oxygen is a heteropolyacid compound containing phosphorus and molybdenum.

第二反応器20の出口R1j及びR2jと分離手段60の入口60iとが、ラインLBにより接続されている。第二反応器20の出口R1j及びR2jは、それぞれ反応器R及びRの出口である。ラインLBは、反応器R及びRの出口から出た流を合流させ、分離手段60に供給するラインである。 The outlets R 1j and R 2j of the second reactor 20 and the inlet 60i of the separating means 60 are connected by a line LB. The outlets R 1j and R 2j of the second reactor 20 are the outlets of the reactors R 1 and R 2 , respectively. The line LB is a line that joins the flows output from the outlets of the reactors R 1 and R 2 and supplies them to the separation means 60.

反応器R及びRは、それぞれの底部の高さA及びAが式(2)を満たすように設置される。反応器R及びRそれぞれの高さH及びHは式(3)を満たす。ここで、高さは、鉛直方向の長さをいう。反応器の底部の高さAは、地表面から反応器の底部までの高さをいい、反応器の高さHは、反応器そのものの高さをいう。
(Amax−Amin)/Aave≦0.02 ・・・(2)
[Amaxは、A〜Aのうちの最大値を示し、Aminは、A〜Aのうちの最小値を示し、Aaveは、A〜Aの平均値を示す。]
(Hmax−Hmin)/Have≦0.02 ・・・(3)
[Hmaxは、H〜Hのうちの最大値を示し、Hminは、H〜Hのうちの最小値を示し、Haveは、H〜Hの平均値を示す。]
Reactor R 1 and R 2, the height A 1 and A 2 of the respective bottoms are installed to satisfy equation (2). The heights H 1 and H 2 of the reactors R 1 and R 2 respectively satisfy the formula (3). Here, the height refers to the length in the vertical direction. The height A at the bottom of the reactor refers to the height from the ground surface to the bottom of the reactor, and the height H of the reactor refers to the height of the reactor itself.
(A max −A min ) / A ave ≦ 0.02 (2)
[A max represents the maximum value of A 1 ~A n, A min denotes the minimum value of A 1 ~A n, A ave represents the average value of A 1 to A n. ]
(H max −H min ) / H ave ≦ 0.02 (3)
[H max represents the maximum value of H 1 ~H n, H min represents the minimum value of the H 1 ~H n, H ave represents the average value of H 1 to H n. ]

aveは、例えば、1〜15mであってもよく、2〜12mであってもよく、4〜10mであってもよい。 A ave may be, for example, 1 to 15 m, 2 to 12 m, or 4 to 10 m.

aveは、例えば、1〜12mであってもよく、2〜10mであってもよく、4〜8mであってもよい。 H ave may be, for example, 1 to 12 m, 2 to 10 m, or 4 to 8 m.

ラインLAの分岐部Xaから反応器Rの入口R1iまでの流路C1iにおける配管の内径D1i及び長さL1iと、ラインLAの分岐部Xaから反応器Rの入口R2iまでの流路C2iにおける配管の内径D2i及び長さL2iとは、式(4a)及び式(4b)の条件を満たす。
(Dmax(i)/Dmin(i))≦1.025 ・・・(4a)
[Dmax(i)は、D1i〜Dniのうちの最大値を示し、Dmin(i)は、D1i〜Dniのうちの最小値を示す。]
(Lmax(i)/Lmin(i))≦1.05 ・・・(4b)
[Lmax(i)は、L1i〜Lniのうちの最大値を示し、Lmin(i)は、L1i〜Lniのうちの最小値を示す。]
The inner diameter D 1i and the length L 1i of the pipe in the flow path C1i from the branch part Xa of the line LA to the inlet R 1i of the reactor R 1 , and from the branch part Xa of the line LA to the inlet R 2i of the reactor R 2 The inner diameter D 2i and the length L 2i of the pipe in the flow path C2i satisfy the conditions of the expressions (4a) and (4b).
(D max (i) / D min (i) ) ≦ 1.025 (4a)
[D max (i) indicates the maximum value of D 1i to D ni , and D min (i) indicates the minimum value of D 1i to D ni . ]
(L max (i) / L min (i) ) ≦ 1.05 (4b)
[L max (i) indicates the maximum value of L 1i to L ni , and L min (i) indicates the minimum value of L 1i to L ni . ]

反応器Rの出口R1jからラインLBの合流部Xbまでの流路C1jにおける配管の内径D1j及び長さL1jと、反応器Rの出口R2jからラインLBの合流部Xbまでの流路C2jにおける配管の内径D2j及び長さL2jとは、式(5a)及び式(5b)の条件を満たす。
(Dmax(j)/Dmin(j))≦1.025 ・・・(5a)
[Dmax(j)は、D1j〜Dnjのうちの最大値を示し、Dmin(j)は、D1j〜Dnjのうちの最小値を示す。]
(Lmax(j)/Lmin(j))≦1.05 ・・・(5b)
[Lmax(j)は、L1j〜Lnjのうちの最大値を示し、Lmin(j)は、L1j〜Lnjのうちの最小値を示す。]
The inner diameter D 1j and the length L 1j of the pipe in the flow path C1j from the outlet R 1j of the reactor R 1 to the merging portion Xb of the line LB, and from the outlet R 2j of the reactor R 2 to the merging portion Xb of the line LB The inner diameter D 2j and the length L 2j of the pipe in the flow path C2j satisfy the conditions of the expressions (5a) and (5b).
(D max (j) / D min (j) ) ≦ 1.025 (5a)
[D max (j) indicates the maximum value of D 1j to D nj , and D min (j) indicates the minimum value of D 1j to D nj . ]
(L max (j) / L min (j) ) ≦ 1.05 (5b)
[L max (j) represents the maximum value among L 1j to L nj , and L min (j) represents the minimum value among L 1j to L nj . ]

本明細書において、配管の内径は、配管の内径における長さ方向の積分の平均値を意味する。また、配管の長さは、配管の中心軸の長さを意味する。   In this specification, the inner diameter of the pipe means an average value of integrals in the length direction at the inner diameter of the pipe. Further, the length of the pipe means the length of the central axis of the pipe.

max(i)は、例えば、200〜1800mmであってもよく、400〜1500mmであってもよく、600〜1300mmであってもよい。 D max (i) may be, for example, 200 to 1800 mm, 400 to 1500 mm, or 600 to 1300 mm.

max(i)は、例えば、1〜40mであってもよく、5〜35mであってもよく、10〜30mであってもよい。 L max (i) may be, for example, 1 to 40 m, 5 to 35 m, or 10 to 30 m.

max(j)は、例えば、200〜1800mmであってもよく、400〜1500mmであってもよく、600〜1300mmであってもよい。 D max (j) may be, for example, 200 to 1800 mm, 400 to 1500 mm, or 600 to 1300 mm.

max(j)は、例えば、1〜40mであってもよく、5〜35mであってもよく、10〜30mであってもよい。 L max (j) may be, for example, 1 to 40 m, 5 to 35 m, or 10 to 30 m.

製造装置100は、設備を更に簡略化し易い観点から、流路C1i及びC2iに同じ流量で同じ流体を通過させたときに、流路C1iにおける入口と出口との間の圧力損失ΔP1i及び流路C2iにおける入口と出口との間の圧力損失ΔP2iが、式(1a)を満たし、流路C1j及びC2jに同じ流量で同じ流体を通過させたときに、流路C1jにおける入口と出口との間の圧力損失ΔP1j及び流路C2jにおける入口と出口との間の圧力損失ΔP2jが、式(1b)を満たすことが好ましい。ここで、同じ流体は、組成、温度及び圧力が同じである流体を意味する。
(ΔPmax(i)−ΔPmin(i))/ΔPave(i)≦0.10 ・・・(1a)
[ΔPmax(i)は、ΔP1i〜ΔPniのうちの最大値を示し、ΔPmin(i)は、ΔP1i〜ΔPniのうちの最小値を示し、ΔPave(i)は、ΔP1i〜ΔPniの平均値を示す。]
(ΔPmax(j)−ΔPmin(j))/ΔPave(j)≦0.10 ・・・(1b)
[ΔPmax(j)は、ΔP1j〜ΔPnjのうちの最大値を示し、ΔPmin(j)は、ΔP1j〜ΔPnjのうちの最小値を示し、ΔPave(j)は、ΔP1j〜ΔPnjの平均値を示す。]
From the viewpoint of facilitating simplification of the facility, the manufacturing apparatus 100 allows the pressure loss ΔP 1i and the flow path between the inlet and the outlet in the flow path C1i when the same fluid is passed through the flow paths C1i and C2i at the same flow rate. When the pressure loss ΔP 2i between the inlet and the outlet in C2i satisfies the formula (1a) and the same fluid is passed through the passages C1j and C2j at the same flow rate, the pressure loss ΔP2i is between the inlet and the outlet in the passage C1j. It is preferable that the pressure loss ΔP 1j and the pressure loss ΔP 2j between the inlet and the outlet in the flow path C2j satisfy the expression (1b). Here, the same fluid means a fluid having the same composition, temperature and pressure.
(ΔP max (i) −ΔP min (i) ) / ΔP ave (i) ≦ 0.10 (1a)
[ΔP max (i) represents the maximum value among ΔP 1i to ΔP ni , ΔP min (i) represents the minimum value among ΔP 1i to ΔP ni , and ΔP ave (i) represents ΔP 1i The average value of ~ ΔP ni is shown. ]
(ΔP max (j) −ΔP min (j) ) / ΔP ave (j) ≦ 0.10 (1b)
[ΔP max (j) represents the maximum value among ΔP 1j to ΔP nj , ΔP min (j) represents the minimum value among ΔP 1j to ΔP nj , and ΔP ave (j) represents ΔP 1j The average value of ~ ΔP nj is shown. ]

分岐部Xaから反応器Rの入口R1iまでの流路C1iと、分岐部Xaから反応器Rの入口R2iまでの流路C2iとは、その形状において、略合同であってもよい。これにより、製造装置100が式(1a)の範囲を満たし易い傾向にある。反応器Rの出口R1jから合流部Xbまでの流路C1jと、反応器Rの出口R2jから合流部Xbまでの流路C2jとは、その形状において、略合同であってもよい。これにより、製造装置100が式(1b)の範囲を満たし易い傾向にある。分岐部Xaから合流部Xbの間に含まれる配管の形状は、分岐部Xa及び合流部Xbを結ぶ線を含む面のうちのいずれかの面に対して略対称であってもよい。 The flow path C1i from the branch part Xa to the inlet R 1i of the reactor R 1 and the flow path C2i from the branch part Xa to the inlet R 2i of the reactor R 2 may be substantially congruent in shape. . Thereby, it exists in the tendency for the manufacturing apparatus 100 to satisfy | fill the range of Formula (1a) easily. Reactor a flow path C1j from the outlet R 1j of R 1 to the merging portion Xb, and the reactor flow passage C2j from the outlet R 2j of R 2 to the joining portion Xb, in its shape, may be substantially congruent . Thereby, it exists in the tendency for the manufacturing apparatus 100 to satisfy | fill the range of Formula (1b) easily. The shape of the piping included between the branch part Xa and the junction part Xb may be substantially symmetric with respect to any one of the surfaces including the line connecting the branch part Xa and the junction part Xb.

分離手段60は、第一の出口から一酸化炭素、二酸化炭素、窒素、アルゴン、軽質成分及び酸素を含む流(F35)を、第二の出口からメタクリル酸及び重質成分を含む流(F31)を、第三の出口からメタクロレインを含む流(F23)を、それぞれ排出する。第一の出口にはラインL35が、第二の出口にはラインL31が、第三の出口にはラインL23が、それぞれ接続されている。   Separation means 60 includes a stream containing carbon monoxide, carbon dioxide, nitrogen, argon, light components and oxygen from a first outlet (F35), and a stream containing methacrylic acid and heavy components from a second outlet (F31). And a stream (M23) containing methacrolein from the third outlet. A line L35 is connected to the first outlet, a line L31 is connected to the second outlet, and a line L23 is connected to the third outlet.

ラインL23は、ラインLAに接続されている。   The line L23 is connected to the line LA.

分離手段60としては、例えば、蒸留塔、抽出塔、吸収塔及びこれらの組み合わせが挙げられる。分離手段60が、1つの蒸留塔からなる場合、ラインL35は蒸留塔の上部に、ラインL31は蒸留塔の下部に、ラインL23は蒸留塔の側面に、それぞれ設けられることが好ましい。   Examples of the separation means 60 include a distillation tower, an extraction tower, an absorption tower, and combinations thereof. When the separating means 60 is composed of one distillation column, it is preferable that the line L35 is provided at the upper part of the distillation column, the line L31 is provided at the lower part of the distillation column, and the line L23 is provided on the side surface of the distillation column.

続いて、本実施形態に係るメタクリル酸の製造方法について説明する。   Then, the manufacturing method of methacrylic acid concerning this embodiment is explained.

(供給源)
イソブチレン及び/又はTBAと酸素とを含むガスの供給源(S0)としてのイソブチレン及び/又はTBAと酸素とを含む流(F10)を用意する。
(supply source)
A stream (F10) containing isobutylene and / or TBA and oxygen as a gas source (S0) containing isobutylene and / or TBA and oxygen is prepared.

流(F10)は、イソブチレン、TBA及び酸素以外の成分を含んでいてもよい。イソブチレン、TBA及び酸素以外の成分としては、例えば、イソプレン等のC5オレフィン類、イソブタン、1−ブテン、2−ブテン(シス,トランス)、プロパン、プロピレン、n−ブタン、メチル−tert−ブチルエーテル、メタノール、ジメチルエーテル、ブタジエン、プロパジエン、ジイソブチレン、窒素、二酸化炭素、一酸化炭素、水及びアルゴンが挙げられる。   Stream (F10) may contain components other than isobutylene, TBA and oxygen. As components other than isobutylene, TBA and oxygen, for example, C5 olefins such as isoprene, isobutane, 1-butene, 2-butene (cis, trans), propane, propylene, n-butane, methyl-tert-butyl ether, methanol , Dimethyl ether, butadiene, propadiene, diisobutylene, nitrogen, carbon dioxide, carbon monoxide, water and argon.

流(F10)中のイソブチレン及び/又はTBAの濃度は、イソブチレン及びTBAの濃度の合計で、例えば、1質量%以上、2質量%以上、又は4質量%以上である。流(F10)中のイソブチレン及びTBAの濃度の合計は、例えば、21質量%以下、19質量%以下、又は17質量%以下である。流(F10)中のイソブチレン及びTBAの濃度の合計は、好ましくは1〜21質量%であり、より好ましくは2〜19質量%であり、更に好ましくは4〜17質量%である。   The concentration of isobutylene and / or TBA in the stream (F10) is, for example, 1% by mass or more, 2% by mass or more, or 4% by mass or more in terms of the total concentration of isobutylene and TBA. The total concentration of isobutylene and TBA in the stream (F10) is, for example, 21% by mass or less, 19% by mass or less, or 17% by mass or less. The total concentration of isobutylene and TBA in the stream (F10) is preferably 1 to 21% by mass, more preferably 2 to 19% by mass, and even more preferably 4 to 17% by mass.

流(F10)中の酸素濃度は、例えば、7質量%以上、8質量%以上、又は10質量%以上である。流(F10)中の酸素濃度は、例えば、24質量%以下、23質量%以下、又は21質量%以下である。流(F10)中の酸素濃度は、好ましくは7〜24質量%であり、より好ましくは8〜23質量%であり、更に好ましくは10〜21質量%である。   The oxygen concentration in the flow (F10) is, for example, 7% by mass or more, 8% by mass or more, or 10% by mass or more. The oxygen concentration in the flow (F10) is, for example, 24% by mass or less, 23% by mass or less, or 21% by mass or less. The oxygen concentration in the stream (F10) is preferably 7 to 24% by mass, more preferably 8 to 23% by mass, and still more preferably 10 to 21% by mass.

また、酸素供給源(S1)としての酸素を含む流(F22)を準備する。   Moreover, the flow (F22) containing oxygen as an oxygen supply source (S1) is prepared.

流(F22)中の酸素の濃度は、例えば、15質量%以上である。流(F22)中の酸素の濃度は、好ましくは16質量%以上であり、より好ましくは17質量%以上であり、更に好ましくは20質量%以上である。流(F22)中の酸素の濃度の上限は、例えば、35質量%とすることができる。流(F22)中の酸素の濃度は、例えば、30質量%以下であってもよく、25質量%以下であってもよい。流(F22)中の酸素濃度は、好ましくは16〜35質量%であり、より好ましくは17〜30質量%であり、更に好ましくは18〜25質量%である。   The concentration of oxygen in the flow (F22) is, for example, 15% by mass or more. The concentration of oxygen in the stream (F22) is preferably 16% by mass or more, more preferably 17% by mass or more, and further preferably 20% by mass or more. The upper limit of the concentration of oxygen in the flow (F22) can be set to 35% by mass, for example. The concentration of oxygen in the flow (F22) may be, for example, 30% by mass or less, or 25% by mass or less. The oxygen concentration in the stream (F22) is preferably 16 to 35% by mass, more preferably 17 to 30% by mass, and still more preferably 18 to 25% by mass.

(反応工程)
流(F10)を第一反応器10に供給し、第一反応器10において流(F10)中のイソブチレン及び酸素を反応させる。イソブチレン及び酸素の反応により得たメタクロレインを含む流(F11)は、ラインLAより排出させる。
(Reaction process)
A stream (F10) is fed to the first reactor 10 where the isobutylene and oxygen in the stream (F10) are reacted. A stream (F11) containing methacrolein obtained by the reaction of isobutylene and oxygen is discharged from the line LA.

第一反応器10の反応温度は、300〜400℃とすることができる。第一反応器10の反応圧力は、0.004〜0.6MPaG(ゲージ圧)とすることができる。   The reaction temperature of the first reactor 10 can be 300 to 400 ° C. The reaction pressure of the first reactor 10 can be 0.004 to 0.6 MPaG (gauge pressure).

第一反応器10から排出された流(F11)には、ラインL23を介してメタクロレインを含む流(F23)を混合し、ラインL22を介して、酸素を含む流(F22)を混合する。これにより、得られた流(F21)を、ラインLAを介して第二反応器20のそれぞれの反応器(R及びR)に供給する。 The stream (F11) discharged from the first reactor 10 is mixed with the stream (F23) containing methacrolein via the line L23, and the stream (F22) containing oxygen is mixed via the line L22. Thereby, the obtained flow (F21) is supplied to each reactor (R 1 and R 2 ) of the second reactor 20 via the line LA.

流(F23)中のメタクロレインの濃度は、好ましくは0.1質量%以上であり、より好ましくは3質量%以上であり、更に好ましくは7質量%以上である。(F23)中のメタクロレインの濃度は、好ましくは32質量%以下であり、より好ましくは23質量%以下であり、更に好ましくは16質量%以下である。流(F23)中のメタクロレインの濃度は、0.1〜32質量%であってもよく、3〜23質量%であってもよく、7〜16質量%であってもよい。流(F23)は、メタクロレイン以外の成分として、例えば、窒素、水及び二酸化炭素を含み得る。   The concentration of methacrolein in the stream (F23) is preferably 0.1% by mass or more, more preferably 3% by mass or more, and further preferably 7% by mass or more. The concentration of methacrolein in (F23) is preferably 32% by mass or less, more preferably 23% by mass or less, and still more preferably 16% by mass or less. The concentration of methacrolein in the flow (F23) may be 0.1 to 32% by mass, 3 to 23% by mass, or 7 to 16% by mass. The stream (F23) may include, for example, nitrogen, water, and carbon dioxide as components other than methacrolein.

第二反応器20では、メタクロレイン及び酸素を反応させてメタクリル酸を得ると共に、ラインLBを介してメタクリル酸を含む流(F30)を排出させる。   In the second reactor 20, methacrolein and oxygen are reacted to obtain methacrylic acid, and a stream (F30) containing methacrylic acid is discharged via the line LB.

流(F30)は、通常、未反応のメタクロレインを含む。流(F30)は、メタクリル酸及びメタクロレイン以外の成分を含み得る。このような成分としては、アクリル酸、アクロレイン、窒素、アルゴン、酸素、水、一酸化炭素、二酸化炭素、アセトアルデヒド、プロピオンアルデヒド、テレフタル酸、マレイン酸、フマル酸、ジアセチル、イソフタル酸、イソ酪酸、メチルフルフラール、酢酸、プロピオン酸等が挙げられる。   The stream (F30) usually contains unreacted methacrolein. The stream (F30) may contain components other than methacrylic acid and methacrolein. Such components include acrylic acid, acrolein, nitrogen, argon, oxygen, water, carbon monoxide, carbon dioxide, acetaldehyde, propionaldehyde, terephthalic acid, maleic acid, fumaric acid, diacetyl, isophthalic acid, isobutyric acid, methyl Furfural, acetic acid, propionic acid and the like can be mentioned.

第二反応器20の反応温度は、200〜350℃とすることができる。第二反応器20における反応圧力は、例えば0.01〜0.3MPaGである。   The reaction temperature of the second reactor 20 can be 200 to 350 ° C. The reaction pressure in the second reactor 20 is, for example, 0.01 to 0.3 MPaG.

(分離工程及びリサイクル工程)
流(F30)は、ラインLBを介して分離手段60に供する。分離手段60で流を分離し、ラインL35から一酸化炭素、二酸化炭素、窒素、アルゴン、軽質成分及び酸素を含む流(F35)を、ラインL31からメタクリル酸及び重質成分を含む流(F31)を、ラインL23からメタクロレインを含む流(F23)を、それぞれ抜き出す。
(Separation process and recycling process)
The stream (F30) is supplied to the separating means 60 via the line LB. The flow is separated by the separation means 60, the flow containing carbon monoxide, carbon dioxide, nitrogen, argon, light components and oxygen (F35) from the line L35, and the flow containing methacrylic acid and heavy components (F31) from the line L31. Are extracted from the line L23 from the flow (F23) containing methacrolein.

メタクロレインを含む流(F23)は、ラインL23を介して流(F11)に合流させる。   The flow (F23) containing methacrolein is joined to the flow (F11) via the line L23.

メタクリル酸の製造装置100は、イソブチレン及び/又はTBAと酸素とからメタクロレインを得る第一反応器10と、メタクロレイン及び酸素を反応させてメタクリル酸を得る複数の第二反応器20(R及びR)と、第一反応器10の出口10j及び第二反応器20(R及びR)の入口に接続され、第一反応器10の出口10jから出た流を分岐して第二反応器20(R及びR)のそれぞれの入口に供給するラインLAと、第二反応器20(R及びR)のそれぞれの出口に接続され、第二反応器20(R及びR)の出口から出た流を合流させるラインLBと、を備え、反応器R及びRそれぞれの底部の高さA及びAが式(2)を満たすように設置され、反応器R及びRそれぞれの高さH及びHが式(3)を満たし、ラインLAの分岐部Xaから反応器R及びRの入口R1i及びR2iまでのそれぞれの流路C1i及びC2iにおける配管の内径D1i及びD2i並びに長さL1i及びL2iが式(4a)及び式(4b)の条件を満たし、反応器R及びRの出口R1j及びR2jからラインLBの合流部Xbまでのそれぞれの流路C1j及びC2jにおける配管の内径D1j及びD2j並びに長さL1j及びL2jが式(5a)及び式(5b)の条件を満たす。これにより、ラインLAにバルブ等を設置せずとも、反応器R及びRに均等に流体を流し易いことから、設備を簡略化し得ると共に、特に複雑な操作をせずとも長期にわたり安定的に運転ができると考えられる。また、上記位置にバルブ等を必ずしも必要としないため、バルブ等のような複雑な形状の部位での配管のつまり等を防止することもできると考えられる。また、メタクリル酸の製造装置100は、複数の第二反応器を有することにより、第二反応器の触媒量を必要量よりも多く充填し易い傾向にある。第二反応器の触媒量を必要量より多く充填することにより、例えば、第一反応器の触媒活性よりも第二反応器の触媒活性の方が先に低下した場合であっても、第二反応器の生産性を保ち易いと考えられる。 The methacrylic acid production apparatus 100 includes a first reactor 10 that obtains methacrolein from isobutylene and / or TBA and oxygen, and a plurality of second reactors 20 (R 1 ) that react with methacrolein and oxygen to obtain methacrylic acid. And R 2 ), and the outlet 10j of the first reactor 10 and the inlet of the second reactor 20 (R 1 and R 2 ), and the flow exiting from the outlet 10j of the first reactor 10 is branched to second reactor 20 (R 1 and R 2) each and a line LA to be supplied to the inlet of being connected to a respective outlet of the second reactor 20 (R 1 and R 2), the second reactor 20 (R 1 And R 2 ), and a line LB for joining the flows coming out of the outlets of the reactors R 1 and R 2 , the bottom heights A 1 and A 2 of each of the reactors R 1 and R 2 are installed so as to satisfy the formula (2), Height H of each of reactors R 1 and R 2 1 and H 2 satisfy the formula (3), and the inner diameters D 1i and D of the pipes in the respective channels C1i and C2i from the branch part Xa of the line LA to the inlets R 1i and R 2i of the reactors R 1 and R 2 2i and lengths L 1i and L 2i satisfy the conditions of the equations (4a) and (4b), and the respective flows from the outlets R 1j and R 2j of the reactors R 1 and R 2 to the junction Xb of the line LB The inner diameters D 1j and D 2j and the lengths L 1j and L 2j of the pipes in the paths C1j and C2j satisfy the conditions of the expressions (5a) and (5b). As a result, it is easy to flow fluid evenly to the reactors R 1 and R 2 without installing valves or the like in the line LA, so that the equipment can be simplified and stable for a long time without any complicated operation. It is thought that it is possible to drive. In addition, since a valve or the like is not necessarily required at the above position, it is considered that piping clogging at a complicatedly shaped part such as a valve can be prevented. Moreover, since the methacrylic acid production apparatus 100 includes a plurality of second reactors, the catalyst amount of the second reactor tends to be filled more than necessary. By filling the amount of catalyst in the second reactor more than necessary, for example, even if the catalytic activity of the second reactor is lower than the catalytic activity of the first reactor, It is considered that the productivity of the reactor is easily maintained.

本実施形態の装置は連続運転性に優れることから、長期運転時の原料及びエネルギーの削減が可能であると考えられる。   Since the apparatus of this embodiment is excellent in continuous operability, it is considered that raw materials and energy can be reduced during long-term operation.

本発明は、上記実施形態に限られず、様々な変形態様が可能である。   The present invention is not limited to the above-described embodiment, and various modifications can be made.

例えば、各ラインに、更に、蒸留塔、抽出塔等の分離精製手段を追加してもよい。   For example, separation and purification means such as a distillation column and an extraction column may be added to each line.

ガスミキサー50bは、省略することもできる。この場合、ラインL22は、ラインL21の配管に直接接続されることができる。   The gas mixer 50b can be omitted. In this case, the line L22 can be directly connected to the piping of the line L21.

ラインL23はあってもなくてもよい。メタクリル酸の製造装置100において、ラインL23は分離手段60に接続されているが、ラインL23は分離手段60に接続されていなくてもよい。すなわち、ラインL23を介してラインLAに供給される流は、分離手段60からリサイクルされる流でなくてもよい。   The line L23 may or may not be present. In the methacrylic acid production apparatus 100, the line L23 is connected to the separation means 60, but the line L23 may not be connected to the separation means 60. In other words, the flow supplied to the line LA via the line L23 may not be a flow recycled from the separation means 60.

第二反応器は、3つ以上の反応器から構成されていてもよい。すなわち、複数の第二反応器R〜Rにおいて、nは3以上であってもよい。この場合、ラインLAの分岐部において、n個の流路に分岐され、ラインLBの合流部においてn個の流路が合流する。そして、反応器R〜Rは、それぞれの底部の高さA〜Aが式(2)を満たすように設置され、かつ、高さH〜Hが式(3)を満たし、ラインLAの分岐部から反応器R〜Rの入口R1i〜Rniまでのそれぞれの流路C1i〜Cniにおける配管の内径D1i〜Dni及び長さL1i〜Lniが式(4a)及び式(4b)の条件を満たし、反応器R〜Rの出口R1j〜RnjからラインLBの合流部までのそれぞれの流路C1j〜Cnjにおける配管の内径D1j〜Dnj及び長さL1j〜Lnjが式(5a)及び式(5b)の条件を満たすような装置とすればよい。 The second reactor may be composed of three or more reactors. That is, in the plurality of second reactors R 1 to R n , n may be 3 or more. In this case, at the branch portion of the line LA, the flow is branched into n flow paths, and the n flow paths merge at the merge portion of the line LB. Then, the reactor R 1 to R n has a height A 1 to A n of each bottom portion is disposed so as to satisfy the equation (2), and satisfies the height H 1 to H n is Equation (3) , The inner diameters D 1i to D ni and the lengths L 1i to L ni of the pipes in the respective flow paths C1i to Cni from the branch portions of the line LA to the inlets R 1i to R ni of the reactors R 1 to R n are expressed by the formula ( 4a) and the equation (4b), satisfying the conditions of the reactors R 1 to R n , and the inner diameters D 1j to D nj of the pipes in the respective flow paths C1j to Cnj from the outlets R 1j to R nj of the reactors R 1 to R n to the junction of the line LB The length L 1j to L nj may satisfy the conditions of the expressions (5a) and (5b).

また、nが3以上の場合においても、流路C1i〜Cniに、同じ流量で同じ流体を通過させたときに、各流路C1i〜Cniにおける入口と出口との間の圧力損失ΔP1i〜ΔPniが、式(1a)を満たし、流路C1j〜Cnjに、同じ流量で同じ流体を通過させたときに、各流路C1j〜Cnjにおける入口と出口との間の圧力損失ΔP1j〜ΔPnjが、式(1b)を満たすことが好ましい。 Even when n is 3 or more, when the same fluid is passed through the channels C1i to Cni at the same flow rate, the pressure loss ΔP 1i to ΔP between the inlet and the outlet in each channel C1i to Cni. When ni satisfies the formula (1a) and the same fluid is passed through the flow paths C1j to Cnj at the same flow rate, the pressure loss ΔP 1j to ΔP nj between the inlet and the outlet in each of the flow paths C1j to Cnj However, it is preferable that Formula (1b) is satisfy | filled.

10…第一反応器、20…第二反応器、50b…ガスミキサー、60…分離手段、100…メタクリル酸の製造装置。   DESCRIPTION OF SYMBOLS 10 ... 1st reactor, 20 ... 2nd reactor, 50b ... Gas mixer, 60 ... Separation means, 100 ... Production apparatus of methacrylic acid.

Claims (3)

イソブチレン及び/又はtert−ブチルアルコールと酸素とからメタクロレインを得る1つの第一反応器と、
メタクロレイン及び酸素を反応させてメタクリル酸を得る複数の第二反応器R〜R(nは2以上の整数を示す)と、
前記1つの第一反応器の出口及び第二反応器R〜Rの入口に接続され、前記1つの第一反応器の出口から出た流を分岐して第二反応器R〜Rのそれぞれの入口に供給するラインLAと、
第二反応器R〜Rのそれぞれの出口に接続され、第二反応器R〜Rの出口から出た流を合流させるラインLBと、を備え、
第二反応器R〜Rそれぞれの底部の高さA〜Aが式(2)を満たすように、第二反応器R〜Rが設置され、
第二反応器R〜Rそれぞれの高さH〜Hが式(3)を満たし、
ラインLAの分岐部から第二反応器R〜Rの入口R1i〜Rniまでのそれぞれの流路C1i〜Cniにおける配管の内径D1i〜Dni及び長さL1i〜Lniが式(4a)及び式(4b)の条件を満たし、
第二反応器R〜Rの出口R1j〜RnjからラインLBの合流部までのそれぞれの流路C1j〜Cnjにおける配管の内径D1j〜Dnj及び長さL1j〜Lnjが式(5a)及び式(5b)の条件を満たし、
aveが2〜12mである、メタクリル酸の製造装置。
(Amax−Amin)/Aave≦0.02 ・・・(2)
[Amaxは、A〜Aのうちの最大値を示し、Aminは、A〜Aのうちの最小値を示し、Aaveは、A〜Aの平均値を示す。]
(Hmax−Hmin)/Have≦0.02 ・・・(3)
[Hmaxは、H〜Hのうちの最大値を示し、Hminは、H〜Hのうちの最小値を示し、Haveは、H〜Hの平均値を示す。]
(Dmax(i)/Dmin(i))≦1.025 ・・・(4a)
[Dmax(i)は、D1i〜Dniのうちの最大値を示し、Dmin(i)は、D1i〜Dniのうちの最小値を示す。]
(Lmax(i)/Lmin(i))≦1.05 ・・・(4b)
[Lmax(i)は、L1i〜Lniのうちの最大値を示し、Lmin(i)は、L1i〜Lniのうちの最小値を示す。]
(Dmax(j)/Dmin(j))≦1.025 ・・・(5a)
[Dmax(j)は、D1j〜Dnjのうちの最大値を示し、Dmin(j)は、D1j〜Dnjのうちの最小値を示す。]
(Lmax(j)/Lmin(j))≦1.05 ・・・(5b)
[Lmax(j)は、L1j〜Lnjのうちの最大値を示し、Lmin(j)は、L1j〜Lnjのうちの最小値を示す。]
A first reactor from isobutylene and / or tert- butyl alcohol and oxygen one to obtain methacrolein,
A plurality of second reactors R 1 to R n (n represents an integer of 2 or more) to obtain methacrylic acid by reacting methacrolein and oxygen;
Connected to the outlet of the one first reactor and the inlets of the second reactors R 1 to R n , the flow exiting from the outlet of the one first reactor is branched to make second reactors R 1 to R a line LA fed to each inlet of n ;
Are connected to respective outlets of the second reactor R 1 to R n, with the line LB to merge the flow exiting from the outlet of the second reactor R 1 to R n, a,
Second reactor R 1 to R n Height A 1 to A n of each bottom so as to satisfy the equation (2), the second reactor R 1 to R n is installed,
The heights H 1 to H n of the second reactors R 1 to R n satisfy the formula (3),
The inner diameters D 1i to D ni and the lengths L 1i to L ni of the pipes in the respective flow paths C1i to Cni from the branch portions of the line LA to the inlets R 1i to R ni of the second reactors R 1 to R n Satisfy the conditions of (4a) and (4b),
The inner diameters D 1j to D nj and the lengths L 1j to L nj of the pipes in the respective flow paths C1j to Cnj from the outlets R 1j to R nj of the second reactors R 1 to R n to the joining portion of the line LB Satisfy the conditions of (5a) and (5b),
An apparatus for producing methacrylic acid, wherein A ave is 2 to 12 m.
(A max −A min ) / A ave ≦ 0.02 (2)
[A max represents the maximum value of A 1 ~A n, A min denotes the minimum value of A 1 ~A n, A ave represents the average value of A 1 to A n. ]
(H max −H min ) / H ave ≦ 0.02 (3)
[H max represents the maximum value of H 1 ~H n, H min represents the minimum value of the H 1 ~H n, H ave represents the average value of H 1 to H n. ]
(D max (i) / D min (i) ) ≦ 1.025 (4a)
[D max (i) indicates the maximum value of D 1i to D ni , and D min (i) indicates the minimum value of D 1i to D ni . ]
(L max (i) / L min (i) ) ≦ 1.05 (4b)
[L max (i) indicates the maximum value of L 1i to L ni , and L min (i) indicates the minimum value of L 1i to L ni . ]
(D max (j) / D min (j) ) ≦ 1.025 (5a)
[D max (j) indicates the maximum value of D 1j to D nj , and D min (j) indicates the minimum value of D 1j to D nj . ]
(L max (j) / L min (j) ) ≦ 1.05 (5b)
[L max (j) represents the maximum value among L 1j to L nj , and L min (j) represents the minimum value among L 1j to L nj . ]
aveが4〜10mである、請求項1に記載のメタクリル酸の製造装置。 The apparatus for producing methacrylic acid according to claim 1, wherein A ave is 4 to 10 m. 流路C1i〜Cniに、同じ流量で同じ流体を通過させたときに、各流路C1i〜Cniにおける入口と出口との間の圧力損失ΔP1i〜ΔPniが、式(1a)を満たし、
流路C1j〜Cnjに、同じ流量で同じ流体を通過させたときに、各流路C1j〜Cnjにおける入口と出口との間の圧力損失ΔP1j〜ΔPnjが、式(1b)を満たす、請求項1又は2に記載のメタクリル酸の製造装置。
(ΔPmax(i)−ΔPmin(i))/ΔPave(i)≦0.10 ・・・(1a)
[ΔPmax(i)は、ΔP1i〜ΔPniのうちの最大値を示し、ΔPmin(i)は、ΔP1i〜ΔPniのうちの最小値を示し、ΔPave(i)は、ΔP1i〜ΔPniの平均値を示す。]
(ΔPmax(j)−ΔPmin(j))/ΔPave(j)≦0.10 ・・・(1b)
[ΔPmax(j)は、ΔP1j〜ΔPnjのうちの最大値を示し、ΔPmin(j)は、ΔP1j〜ΔPnjのうちの最小値を示し、ΔPave(j)は、ΔP1j〜ΔPnjの平均値を示す。]
When the same fluid is passed through the channels C1i to Cni at the same flow rate, the pressure losses ΔP 1i to ΔP ni between the inlets and the outlets of the channels C1i to Cni satisfy the formula (1a),
When the same fluid is passed through the flow paths C1j to Cnj at the same flow rate, the pressure losses ΔP 1j to ΔP nj between the inlet and the outlet in each of the flow paths C1j to Cnj satisfy Expression (1b). Item 3. An apparatus for producing methacrylic acid according to Item 1 or 2.
(ΔP max (i) −ΔP min (i) ) / ΔP ave (i) ≦ 0.10 (1a)
[ΔP max (i) represents the maximum value among ΔP 1i to ΔP ni , ΔP min (i) represents the minimum value among ΔP 1i to ΔP ni , and ΔP ave (i) represents ΔP 1i The average value of ~ ΔP ni is shown. ]
(ΔP max (j) −ΔP min (j) ) / ΔP ave (j) ≦ 0.10 (1b)
[ΔP max (j) represents the maximum value among ΔP 1j to ΔP nj , ΔP min (j) represents the minimum value among ΔP 1j to ΔP nj , and ΔP ave (j) represents ΔP 1j The average value of ~ ΔP nj is shown. ]
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