CN102361841A - Process for production of p-dichlorobenzene - Google Patents
Process for production of p-dichlorobenzene Download PDFInfo
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- CN102361841A CN102361841A CN2010800134167A CN201080013416A CN102361841A CN 102361841 A CN102361841 A CN 102361841A CN 2010800134167 A CN2010800134167 A CN 2010800134167A CN 201080013416 A CN201080013416 A CN 201080013416A CN 102361841 A CN102361841 A CN 102361841A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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Abstract
Provided is a process for the production of p-dichlorobenzene using a full size facility, which can be carried out by stable operation, and by which the objective substance can be obtained in a high yield. Specifically provided is a process for the production of p-dichlorobenzene by chlorinating a starting material consisting of benzene and/or monochlorobenzene with chlorine gas, which comprises introducing the starting material and the chlorine gas into a reactor wherein a zeolite-containing catalyst is put as a fixed bed. The catalyst can be obtained by forming using an alumina-based forming base material.
Description
Technical field
The present invention relates to the method for manufacture of santochlor, particularly relate to at least one side of benzene (following also be expressed as " Bz ") and monochloro-benzene (following also be expressed as " MCB ") as raw material, with zeolite as catalyzer, utilize chlorine to carry out the method that santochlor (following also be expressed as " p-DCB " or " PDCB ") made in chlorination.In addition, in this manual, " zeolite catalyst " expression " catalyzer that contains zeolite ".
Background technology
P-DCB is as the raw material of medicine, agricultural chemicals; And himself is as sterilant, insect-proof agent; Further the raw material as polyphenylene sulfide (PPS) is the high compound of commercial value.
In the past, for p-DCB, known had a method of manufacture of Lewis acids such as iron(ic)chloride, antimony pentachloride being carried out liquid phase chlorination as catalyzer to benzene and/or monochloro-benzene.The active height of iron(ic)chloride, the chlorine transformation efficiency reaches more than 99.99%, and the unreacted chlorine in the by-product salt acid gas is the residual degree of denier.But, for selection rate, be at most about 60% when using catalyzer separately as the para-orientation thing of target compound, add promotor and then can be increased to about 75%.
In recent years, as being the method that mode more than 90.4% (904%) is made p-DCB with selection rate, shown in patent documentation 1, patent documentation 2 etc., the method for zeolite L as catalyzer of using disclosed.But, use zeolite to be the method for laboratory level, according to thinking that not being is the concrete grammar that can be used as the degree of actual device running as the method for catalyzer.
The prior art document
Patent documentation
Patent documentation 1: the special public clear 63-12450 communique of Japan
Patent documentation 2: TOHKEMY 2001-213815 communique
Non-patent literature
Patent Document 1: Light Gangzuo Chibu "Nano pts a ra su athlete Forward-ra ィ Suites catalyst surface design と modulation (nanoporous zeolite catalyst surface design and preparation method)", Chemical? Engineering, 2008 April, 2008 issue, pp.286-289
Summary of the invention
The problem that invention will solve
The problem that the present invention will solve is to provide following method: when making p-DCB (santochlor), under situation, can obtain target compound with high yield as the actual device running, and can steady running.
Can recognize other problems through following explanation.
The method that is used to deal with problems
The present invention who has solved this problem is described below.
[the described invention of claim 1]
A kind of method of manufacture of santochlor; It is as raw material and use chlorine to carry out the method that santochlor is made in chlorination with benzene and monochloro-benzene at least a; This method of manufacture is characterised in that; Above-mentioned raw materials and above-mentioned chlorine are directed in the reactor drum that the catalyzer that contains zeolite is housed in the mode with fixed bed, and the moulding base that above-mentioned catalyzer utilization is principal constituent with the alumina sol carries out moulding to zeolite and obtains.
[the described invention of claim 2]
A kind of method of manufacture of santochlor; It is as raw material and use chlorine to carry out the method that santochlor is made in chlorination with benzene and monochloro-benzene at least a; This method of manufacture is characterised in that; In the interior reactor drum that the catalyzer that contains zeolite is housed, the unreacted chlorine of above-mentioned raw materials, chlorine and/or back segment is supplied in the reactor drum of first section with multistage; The resultant of reaction of leading portion is supplied in the reactor drum of secondary segment; The chlorine of excess quantity is supplied in the later reactor drum of secondary segment; Formation reaction thing by terminal section obtains santochlor.
[the described invention of claim 3]
A kind of method of manufacture of santochlor; It is as raw material and use chlorine to carry out the method that santochlor is made in chlorination with benzene and monochloro-benzene at least a; This method of manufacture is characterised in that; In the interior reactor drum that the catalyzer that contains zeolite is housed, above-mentioned raw materials, chlorine are supplied in the reactor drum of first section with multistage; The resultant of reaction of leading portion is separated into unreacting material and resultant, unreacting material is returned in the reactor drum of leading portion, resultant is supplied in the reactor drum of secondary segment; Chlorine is supplied in the later reactor drum of secondary segment; Resultant of reaction by terminal section obtains santochlor.
[the described invention of claim 4]
A kind of method of manufacture of santochlor; It is as raw material and use chlorine to carry out the method that santochlor is made in chlorination with benzene and monochloro-benzene at least a; This method of manufacture is characterised in that, above-mentioned raw materials and above-mentioned chlorine are directed into to be equipped with in the reactor drum of the catalyzer that contains zeolite in the mode of starching the attitude bed.
[the described invention of claim 5]
The method of manufacture of each described santochlor of claim 1～3 wherein, is directed at least a heat-eliminating medium of methyl chloride and monochloroethane in each section of said reactor drum, and the temperature that make said heat-eliminating medium evaporation, suppresses said chlorination reaction rises.
[the described invention of claim 6]
The method of manufacture of the described santochlor of claim 5, wherein, the vaporised gas composition of said heat-eliminating medium utilizes this phlegma as said heat-eliminating medium in the reactor drum condensed exterior again.
[the described invention of claim 7]
The method of manufacture of claim 2 or 3 described santochlor, wherein, with being loaded in the said reactor drum in the said mode of catalyzer that contains zeolite with fixed bed.
[the described invention of claim 8]
The method of manufacture of each described santochlor of claim 2～4, wherein, the moulding base that the said catalyzer utilization that contains zeolite is principal constituent with the alumina sol carries out moulding to zeolite and obtains.
[the described invention of claim 9]
The method of manufacture of each described santochlor of claim 1～4, wherein, said zeolite is the proton type zeolite.
[the described invention of claim 10]
The method of manufacture of each described santochlor of claim 1～4, wherein, said zeolite is a zeolite beta.
[the described invention of claim 11]
The method of manufacture of each described santochlor of claim 1～4, wherein, said zeolite is a MFI type zeolite.
[the described invention of claim 12]
The method of manufacture of each described santochlor of claim 1～3 wherein, is utilized to fall to flow to make said raw material and chlorine circulation.
[the described invention of claim 13]
The method of manufacture of each described santochlor of claim 1～4, wherein, said chlorination reaction is that 40～130 ℃, pressure are to carry out below the 10atm in temperature.
[the described invention of claim 14]
The method of manufacture of the described santochlor of claim 1, wherein, said reactor drum has multistage; Chlorine is supplied in each reactor drum with mode arranged side by side; Said raw material and chlorine are supplied in the reactor drum of first section; The resultant of reaction of leading portion is supplied in the reactor drum of secondary segment; Chlorine is supplied in the later reactor drum of secondary segment with mode arranged side by side; Resultant of reaction by terminal section obtains santochlor.
[the described invention of claim 15]
The method of manufacture of the described santochlor of claim 4, wherein, said reactor drum has multistage; Said raw material, chlorine are supplied in the reactor drum of first section; The resultant of reaction of leading portion is supplied in the reactor drum of secondary segment; Chlorine is supplied in the later reactor drum of secondary segment with mode arranged side by side; Resultant of reaction by terminal section obtains santochlor.
The invention effect
According to the present invention, can eliminate the shortcoming that selectivity is low, catalyst separating reclaims related device burden as the p-DCB in the homogeneous catalysts such as iron(ic)chloride of prior art, can steady running when turning round as actual device.
Description of drawings
Fig. 1 is the schema of the 1st embodiment of the present invention.
Fig. 2 is the schema of base feed, chlorine under the upwelling condition.
Fig. 3 is illustrated in to have used respectively with under silicon dioxide gel, the situation of alumina sol as the BEA of moulding base the graphic representation of DCB productive rate, para-selectivity.
Fig. 4 is illustrated under the situation of having used the silica-alumina catalyzer graphic representation of DCB productive rate, para-selectivity.
Fig. 5 is illustrated in to have used with under the situation of alumina sol as the BEA of moulding base, MFI, USY the graphic representation of DCB productive rate, para-selectivity respectively.
Fig. 6 is the metallic cation replacement rate variation of expression along with the IX point of zeolite catalyst, the graphic representation of the variation of DCB productive rate, para-selectivity.
The graphic representation that Fig. 7 has been to use the reaction under the situation of zeolite catalyst to carry out.
Fig. 8 is that to be illustrated in temperature of reaction be that 80 ℃, liquid phase cools temperature are under 58 ℃ the condition, representes that by the relation of the ratio of pressure and chloroform/benzene the explanation of recovery etc. uses graphic representation.
Fig. 9 is the schema of the 2nd embodiment of the present invention.
Figure 10 is the schema of the 3rd embodiment of the present invention.
Figure 11 is the schema of the 4th embodiment of the present invention.
Figure 12 is the graphic representation that the reaction in the 2nd embodiment of the present invention is carried out.
Figure 13 is the graphic representation of the chlorination degree of the resultant of reaction in the 2nd embodiment of the present invention.
Figure 14 is the comparative graph of the para-selectivity under embodiment of the present invention and the isolating condition of not carrying out resultant of reaction.
Figure 15 is the summary pie graph of the reaction unit of existing example (comparative example: use homogeneous catalyst).
Figure 16 is the composition history curve figure of each material in the existing example (use homogeneous catalyst).
Figure 17 is the optionally graphic representation of the p-DCB in the existing example (use homogeneous catalyst).
Figure 18 is the graphic representation that is accompanied by chlorination p-DCB productive rate in the existing example (use homogeneous catalyst).
Figure 19 is the graphic representation of temperature of reaction to optionally influencing in the existing example of expression (use homogeneous catalyst).
Figure 20 is the graphic representation of catalytic amount to optionally influencing in the existing example of expression (use homogeneous catalyst).
Embodiment
(the basic design of invention)
As stated, during homogeneous catalysts such as use iron(ic)chloride, not only the p-DCB selectivity is low, and the burden of the separating and reclaiming device of catalyzer also can become big.In the present invention,, can improve the selectivity of p-DCB through using zeolite catalyst, and, through using solid catalyst, catalyzer can be utilized again.
In addition, as stated, chlorination reaction is fierce thermopositive reaction.By the way, if do not dispel the heat, then can be warming up to 400～500 ℃ simply.Therefore, need suppress temperature rightly and rise, in certain temperature range, keep on the go.If temperature is low excessively, can cause then that viscosity uprises, the pressure-losses increases.On the contrary, under the pyritous situation, chlorine is dissolved into to speed limit (rule speed), and reaction is suppressed.In addition, the boiling point of benzene is 80.1 ℃, and under the condition of benzene evaporation, reaction can be suppressed in the nature of things.And, thereby also need confirm to be maintained suitable temperature of reaction (speed of response) to reaction pressure.
As the method that suppresses thermopositive reaction; According to thinking method that cooling end is set is arranged in reactor drums such as chuck and coil pipe, through using method that a large amount of solvents suppresses the temperature rising (as candidate's solvent; Thinking has 1; 2-ethylene dichloride or MCB) and through and the method for carrying out with cooling end and solvent etc., also can use these methods certainly.Yet; Although under preferred reaction conditions (40～130 ℃, below the 10atm), be gas-liquid mixed phase state; But whole heat transfer rate for reacting part-metal part-cooling end; Owing to compare air phase volume with liquid phase volume and have overwhelming advantage, so the heat transfer rate of reacting part becomes the mastery factor, and overall heat transfer coefficient is merely 10～30kcal/m
2About hr ℃, under this condition, need huge heat transfer area, be difficult to specialize as reactor drum.
Therefore, in the present invention, the direct cooling mode that has proposed to utilize the vaporization heat that cools off solvent is as preferred condition.It is present in the reaction system through making the compound that has with the boiling point of reaction conditions same degree, makes the vaporization heat that accompanies with this compound evaporation be transferred to this compound, can absorb the huge reaction heat that is produced thus.
The compound of evaporation can utilize through condensation again, during condensation, can use and can guarantee that overall heat transfer coefficient is 600～1100kcal/m
2Hr ℃ shell-tube type general external heat exchangers such as (shell and tube).
For the compound that can in this direct heat-eliminating medium, use; Not react is condition; The compound that is suitable for p-DCB synthetic chlorination reaction has methylene dichloride (40.2 ℃ of Tb), trichloromethane (61.1 ℃ of Tb), tetrachloromethane (76.8 ℃ of Tb), 1.1-ethylene dichloride (57. ℃ of Tb), 1; 1,1-trichloroethane chloromethane alkanes, chloroethene alkanes such as (73.9 ℃ of Tb).Thereby can consider to come the selected pressure condition that is fit to carry out stable temperature treatment with the boiling point of direct heat-eliminating medium to desired temperature of reaction and benzene.
In the operation of following explanation; Enumerated and adopted the example of the trichloromethane (another name chloroform) of atmospheric boiling point to describe with 61 ℃; But also can use above-mentioned other chloromethane alkanes or chloroethene alkanes, confirm that in addition these compounds also can use more than 2 kinds.
In addition, the present invention uses benzene and/or chlorobenzene and chlorine, uses above-mentioned direct heat-eliminating medium (being chloroform in the following example) simultaneously.It is put in order, be described below.
1) raw material and raw material impurity: benzene, chlorobenzene, chlorine
2) solvent solution and impurity thereof: chloroform, water
3) resultant of reaction: monochloro-benzene, dichlorobenzene, trichloro-benzene, hydrogenchloride
Composition to above is considered, suitable separation means is made up, and obtains the target santochlor.
If an example of reaction formula is represented, then be described below.
Bz(C
6H
6)→MCB(C
6H
5Cl)→PDCB、MDCB、ODCB(p-C
6H
4Cl
2、o-C
6H
4Cl
2、m-C
6H
4Cl
2)→TCB(C
6H
3Cl
3)
PDCB building-up reactions mechanism: ◇
C
6H
6+Cl
2→C
6H
5Cl+HCl (1)
C
6H
5Cl+Cl
2→p-C
6H
4Cl
2+HCl?(2)
C
6H
5Cl+Cl
2→o-C
6H
4Cl
2+HCl (3)
C
6H
5Cl+Cl
2→m-C
6H
4Cl
2+HCl (4)◇
p-C
6H
4Cl
2+Cl
2→C
6H
3Cl
3+HCl (5)
o-C
6H
4Cl
2+Cl
2→C
6H
3Cl
3+HCl (6)
C
6H
3Cl
3+Cl
2→C
6H
2Cl
4+HCl (7)
If, then be described below to representing as an example of the not chlorine addition reaction of preferred side reaction.
Based on the tetrachloro tetrahydrobenzene of the chlorine addition reaction of benzene and the generation of lindane:
C
6H
6+2Cl
2→C
6H
6Cl
4 (8)
C
6H
6+3Cl
2→C
6H
6Cl
6 (9)
The material that poisons that tetrachloro tetrahydrobenzene that not preferred side reaction is generated and lindane might become catalyzer is worried the deterioration that it may cause catalyzer.
Think that in addition in this reaction, the moisture of trace is necessary for showing ionic reaction in the zeolite catalyst.But necessary above moisture can cause the corrosion of device, and can relate to reaction, might reduce reactive and the generation by product.Therefore, expectation is suitably adjusted the moisture in the raw material.
(optimal way of zeolite catalyst)
In the present invention, use the catalyzer that contains zeolite.As this zeolite, can enumerate L type, ZSM-5 (MFI), the MCM-22 (MWW) of fine pore type in the erionite, saspachite (ォ Off レ タ ィ ト), ferrierite (Off ェ リ ェ ラ ィ ト) of little fine pore type; The β type (BEA) of big fine pore type, mordenite (MOR), X type, T type (FAU) etc., these zeolites all can use.The L type of fine pore type, ZSM-5 (MFI), MCM-22 (MWW) in can preferably using; β type (BEA), mordenite (MOR), X type, T type (FAU), the Y type (USY) of big fine pore type.
When zeolite is monomer; It can't moulding, becomes the diameter small powder of
approximately.When in slurry attitude bed, using, zeolite catalyst of the present invention can use with the form of powder, and the particle that also can manufacture diameter 0.8～3.2mm uses with the mode of formed body.In addition, also can be shaped to special shapes such as ring-type, four leaves (Network ヮ one De ロ one Block) shape, gilled rings shape as required.If consider and carry out recycling after using zeolite catalyst, then preferably use with the mode of the formed body of easy recovery more.As for molding a molded zeolite base material (molding additive), for example, nano-particle size silica airgel, alumina sol, preferably using a single component (non-consolidated) alumina sol.DCB productive rate, the para-selectivity of the catalyzer that obtains using alumina sol, silicon dioxide gel that proton type BEA is carried out moulding respectively compare; The result can distinguish; Though para-selectivity is not found big difference; But utilize the catalyzer through the alumina sol moulding, the long period stably obtains high yield (Fig. 3) relatively.In the prior art, the moulding of zeolite is to use silicon dioxide gel to carry out, and owing to the atopic that on zeolite surface, is difficult to form new IX point, can not hinder zeolite, is preferred therefore.But in the reaction of this mode, through using alumina sol, para-selectivity can not descend, and the stability of catalyzer self improves.Therefore hinted that above-mentioned reaction does not occur over just in the hole of zeolite, generation has also been arranged at the IX point that is formed at the preformed catalyst surface by aluminum oxide.If the reaction occur over just in the hole of zeolite, the deterioration by the catalyzer due to the obturation of hole then possibly take place, and if the reaction of catalyst surface, then with compared in the past, degradation speed also can reduce.
As stated, if the aluminum oxide of zeolite surface is above-mentioned IX point, then also we can say the certainty of not using zeolite.But if use the silica-alumina catalyzer to carry out same reaction, then productive rate becomes very low, demonstrates catalyst activity very low (Fig. 4).In addition, compare during with the use zeolite, para-selectivity also is lower value.Distinguish thus: in p-DCB generates, keep high yield, selectivity in order to make catalyzer with aluminum oxide, must be with special skeleton that zeolite was had as carrier.In non-patent literature 1, shown the catalyst activity that the structure of utilizing zeolite can improve aluminum oxide clearly.
Zeolite framework has a great difference according to the difference of zeolite type.To in the zeolite as in the alumina sol preformed catalyst of the ZSM-5 (MFI) that uses typically of the zeolite of fine pore, big fine pore, β type (BEA), Y type (USY); Its activity is compared; The result can distinguish; As shown in Figure 5, DCB productive rate low (because in side reaction, generating TCB (not shown) in a large number) when using USY; And relative therewith, when using BEA, MFI, demonstrate high DCB productive rate.The difference that has hinted the surface tissue due to the skeleton structure of zeolite has caused influence to the catalyst activity of aluminum oxide.In the present invention, we can say and especially preferably use ZSM-5 (MFI), β type (BEA).
Be that the moulding base of principal constituent is selected to be 10 quality %～50 quality %, to be preferably the amount of 15 quality %～30 quality % with respect to total catalyst levels with the aluminum oxide.If less than 10 quality %, the associativity variation of then catalyst activity step-down, and zeolite and moulding base.If more than the 50 quality %, then the volume of catalyzer increase to volume required more than, can't give play to simultaneously the characteristic of above-mentioned zeolite framework, catalyst activity still can descend.
The zeolite of the zeolite catalyst of this mode more preferably uses proton type.Its reason is, has been found that if use by metallic cation (for example sodium ion) the IX point of zeolite has been carried out substituted zeolite, though then initial activity improves, and catalyst activity can descend rapidly at short notice (not shown).
(other modes of zeolite catalyst)
Following discloses do not have to use with aluminum oxide and be the zeolite catalyst in the example of the moulding base of principal constituent.In this mode, use the zeolite that has replaced IX point by metallic cation.
In this mode with at least a portion of the IX point of zeolite by metallic cation, preferably used by the occupied state of sodium cation.Particularly under more than at least 10% of IX point, preferred 10%～85% of zeolite of preformed catalyst that with the zeolite the is principal constituent situation occupied by above-mentioned metallic cation, effect big (Fig. 6).If the occupied ratio of above-mentioned metallic cation, can produce then that the efficient of above-mentioned chlorination reaction reduces less than 10% or side reaction increase etc.
For at least a portion of the IX point that makes zeolite is in by metallic cation, particularly by the occupied state of sodium cation, can utilizes known method to carry out IX and use.For IX is sodium cation, generally carry out through the aqueous solution that uses sodium salt, the exchange operations of preferably using sodium chloride aqueous solution to carry out more than 2 times.
And distinguish that under the situation of homogeneous catalysts such as iron(ic)chloride, reaction is not only carried out with mode progressively, also carries out with parallel mode; And relative therewith, for zeolite catalyst, reaction almost 100% is carried out (Fig. 7) with mode progressively.According to thinking that this is because under the situation of homogeneous catalyst, in the residual stage that benzene is arranged, likewise arbitrarily and catalyzer formation complex compound and reacting as the monomer of resultant or disome and benzene; And in contrast, owing in zeolite catalyst, there is the resistance of the diffusion of reaction molecular, therefore thinks to react according to benzene, monomer, disome, trisome, this order that spreads easily of limbs and progressively carry out.
Preformed catalyst to being principal constituent with these 2 kinds of zeolites respectively compares, and the result can know, is that the performance of the catalyzer of principal constituent exists in circulation system and can't give full play to such problem points with ZSM-5 (MFI) zeolite, and zeolite beta is then more excellent.
For resistance, in requiring in the interior reactor drum that preformed catalyst is housed, can to stablize the circulation system of use, can cause active remarkable reduction for the diffusion that improves the zeolite catalyst that selectivity selects.In addition; For based on the interior result of flow type of reactor drum that the preformed catalyst that is principal constituent is housed with the zeolite beta; Can know and compare based on the step result with the slurry reactor of preformed catalyst powderised, be that activity or selectivity are all more excellent.
In the reactor drum is the zeolite beta of the preformed catalyst of staple for interior being loaded on the zeolite, its SiO
2/ Al
2O
3Ratio be preferably 14～100 (more preferably 16～50).According to thinking; If less than 14; Then have octahedral aluminium in crystallization of zeolites or particulate outer surface part; Its separately or through with the interaction of the functional group that is present in outer surface of zeolite, thereby form the sour site of the various intensity of carrying out the such outer surface of zeolite of non-selective chlorination reaction, the alkali site that promptly forms metal (sodium) cationic ion exchange spot or carry out the chlorine addition reaction, therefore not preferred.In addition, if greater than 100, then the concentration of the active site in the pore of zeolite reduces; Diffusion length is elongated; Cause reaction to proceed to till the trisome thus, and owing to the delay of resultant makes the pore internal diffusion of raw molecule receive resistance, thereby hindered the carrying out of goal response.
In addition, in order to make IX proceed to targeted degree at short notice, Yi Bian preferably the aqueous solution of sodium salt is exchanged the exchange operations of carrying out more than 2 times on one side.Further, in the operation, select to make the pH of solution side to finish simultaneously the sodium-chlor that is adhered to be cleaned, remove the method for carrying out the last time in acidic side.For the concentration of aqueous solution of sodium-chlor at this moment or the number of times of amount and exchange operations, can suitably select.
Yet according to thinking, it is to utilize sodium-chlor to carry out the point that IX becomes sodium cation by the occupied state of sodium cation that at least a portion in the IX point of zeolite is in.As such site, when proton type, be considered to demonstrate highly acid Br.
By the way; State for the zeolite of the zeolite catalyst of making this mode; The preformed catalyst that with zeolite or with the zeolite is principal constituent is made into proton type; Utilize the strong acid salt of metal, particularly sodium to carry out IX then, make the occupied by sodium cation more than at least 10% of IX point, it is effective being made into such state.
In addition, in order to make the zeolite catalyst of this mode, preferably can not form the matrix (matrix) of new IX point with zeolite.As this preferred matrix, can use silicon-dioxide aerosol of nanoparticle size for example etc. separately.If use the moulding base more than 2 kinds simultaneously, then can obtain new IX point at zeolite surface, might cause detrimentally affect to catalyst activity.In addition, since zeolite mainly by SiO
2Constitute the therefore preferred SiO that uses
2As shaping assistant.Also can remove the Al of zeolite surface through s.t., use SiO then
2As shaping assistant.
As the effect of shaping assistant, must be supplied in the formed body with the mode of the catalyst performance that do not damage zeolite, and will have and industry to go up the intensity of using.As the amount of this moulding base, select the amount of 10 quality %～50 quality %, preferred 15 quality %～35 quality %.If less than 10 quality %, the associativity variation of zeolite and moulding base then.If more than the 50 quality %, then the volume of catalyzer increase to volume required more than, simultaneously receive reaction raw materials easily and be difficult to arrive to this diffusion influence of zeolite activity point.
(summary of reaction unit)
In the present invention, be loaded in the reactor drum in the zeolite catalyst.Owing to there is the deterioration of zeolite catalyst, therefore the expectation reactor drum is set to multistage (minimum 2 sections) and exchanges use.Zeolite catalyst can use with the mode of fixed bed, makes the circulation of raw material and chlorine, also can use (Figure 11) with the mode of slurry attitude bed in addition.Through using zeolite catalyst, can suppress temperature effectively and rise, and can in certain temperature range, keep on the go with the mode of slurry attitude bed.
Use with the mode of fixed bed under the situation of catalyzer,, more preferably adopt the circulation (Fig. 1) of falling stream though also can utilize upwelling to make said raw material, chlorine circulation (Fig. 2).If utilize upwelling to circulate; Then owing to be the external phase of liquid in the reactor drum; Therefore leave chlorine being dissolved into to resultant of reaction in speed limit or the liquid in solution and the such problem of backmixing occurs; But, then become the external phase of gas in the reactor drum, thereby can solve said problem if carry out through falling stream.
At this moment, expectation is guaranteed evenly to flow as the dispersion of the gas phase at chlorine center and liquid phase, gets rid of backmixing.The flow pattern of gas-liquid multi-phase flow can change because of the reactor drum footpath of being adopted.The flow pattern to be used for the pulsatile flow (Pulsing? And? Foaming? Flow) or trickle (specified within the article flow, Gas-continuous? Or? Tricking? Flow), preferably a trickle.Pulsating flow is meant that part and little part that liquid hold-up is big replace the mobile state; Drip is a liquid because gravity flows down from granules of catalyst with membranaceous, and gas is external phase and flows through this spatial state.Along with the flow velocity change of gas-liquid multi-phase flow is big, flow pattern becomes drip from pulsating flow.
In addition, the hop count of reactor drum fixed bed has multistage, preferably has 3 sections.Under the deterioration of the solid catalyst situation how,, cause active site to disappear because the worsening reason material flows into from inlet portion.As the countermeasure that is directed to this, can enumerate following manner: each fixed bed is connected in series with 3 individual slots, if thereby deterioration takes place then replace to connect use circularly.Through being set to multistage, the addition of chloroform also can use by turns, chloroform amount that can the inhibition system internal recycle.
As temperature of reaction, if temperature is low excessively, then viscosity uprises, the pressure-losses increases.On the contrary, under the pyritous situation, chlorine is dissolved into and is speed limit, and reaction is suppressed.Therefore, be 40～130 ℃ as temperature of reaction, more preferably 55～90 ℃.
As reaction pressure, as with 80 ℃ of shown in Figure 8 as temperature of reaction example, from being correlated with of the addition of chloroform, the PDCB liquid phase recovery, expectation is that 950～1450Torr is (if temperature of reaction is then to be same in 55～90 ℃ the scope.)。
Can make to judge by Fig. 8.That is, temperature of reaction if do not improve the ratio of chloroform/benzene, then can't be kept in case the pressure that turns round uprises in (1); (2) more than the pressure of certain service temperature, chloroform can not evaporate, and in order to keep this temperature, needs a large amount of chloroforms; (3) on the contrary, below the pressure of certain service temperature, chloroform all evaporates.At this moment, PDCB evaporates equally; (4) therefore, the condition that chloroform or PDCB remain at the bottom of the tower of reactor drum is appropriate, preferably in the recovery of chloroform or PDCB can not produce the zone of big influence to the ratio of chloroform/benzene, operate; Expectation is for the ratio of chloroform/benzene is 16～20, the PDCB recovery is 90～95% zone.
After the reaction,, need cool off for chloroform and the resultant of reaction that has carried out adiabatic evaporation reclaimed, in secondary segment, utilizes again.For with chloroform condensation cooling, can use general external heat exchangers such as shell-tube type.
PDCB also can vaporize, but because the fusing point of PDCB is 53 ℃, so the environment of the independent condensation of PDCB can not be set at below 53 ℃.But, arrive through experimental verification, because chloroform if therefore have chloroform, then separating out of PDCB can not taken place to the effect that PDCB has played solvent yet near normal temperature.It is not impossible being reduced to below 40 ℃.
Directly the trichloromethane (chloroform) of heat-eliminating medium reacts with chlorine and is converted into tetrachloromethane.Therefore, thus expectation separates tetrachloromethane to be removed to tetrachloromethane can be accumulated in the trichloromethane circulating system from trichloromethane.
Then, operation is constructed in desired operation remark additionally.
In the resultant of reaction in reactor drum, contain by product (hydrocarbon compound) and hydrogenchloride.Because the boiling point of hydrogenchloride is-85 ℃, liquids recovery is difficulty very, and therefore the mode with the aqueous solution reclaims.The hydrogen cloride concentration expectation of reclaiming, then can easily be reclaimed if be the degree of 35%HCl for high as far as possible concentration.
That is, the resultant of reaction in the reactor drum is delivered to hydrogenchloride removes tower, the cat head of removing tower from hydrogenchloride with hydrogenchloride with separate with hydrocarbon compound that it accompanies; Hydrogenchloride and a spot of hydrocarbon compound of accompanying with it are delivered to cooling tower; In this cooling tower; To carry out the refrigerative water-phase component through the accessory condensing surface intersperses among in the tower and cools off; Thereby at the bottom of cooling tower, separate into water and hydrocarbon compound, obtain the 35%HCl aqueous solution with the mode of this isolating water-phase component.For separated hydrocarbon compound, utilize the knockout tower of back segment to separate into water and hydrocarbon compound, hydrocarbon compound is utilized again.
For the resultant of reaction that accumulates at the bottom of hydrogenchloride is removed the tower of tower,,, carry out commercialization Yi Bian target p-DCB crystallization is separated out on one side can remove TCB, m-DCB, o-DCB afterwards.
The appropriate location that in addition, can the liquid in the system be returned to in-process utilizes again.
(the 1st embodiment)
Then, embodiment of the present invention is described.
Fig. 1 representes the 1st embodiment of the present invention.
10 is reactor drum, is 3 sections formations in embodiment.For benzene 1, utilize the not shown moisture means of removing in advance moisture to be removed the back as required and supply with from the cat head of the 1st section reactor drum 10 as raw material.
For chlorine 2, in the reactor drum 10,10,10 of each section, supply with mode arranged side by side from its cat head.In each reactor drum 10,10,10, set up condensing surface 12,12,12.Chloroform (heat-eliminating medium) 3 delivered to mixing tank 14 by storage tank, be supplied to by its cat head through pump 16 in the 1st section the reactor drum 10.In addition, recovery chloroform 3A that the back operation of utilizing the not shown treatment scheme of detailed content is reclaimed and benzene 1 are together supplied with from the cat head of the 1st section reactor drum 10.In addition, the recovery chloroform 3B that the back operation of likewise utilizing the not shown treatment scheme of detailed content is reclaimed is supplied in the said mixing tank 14.
In each reactor drum 10,10,10, zeolite catalyst 18 (formed body) is housed in the mode with fixed bed, utilize to fall to flow to make raw material (benzene), chlorine circulation.Be provided with cooling with chuck 11 at reactor drum 10 perisporiums, utilize heat-eliminating medium such as water to cool off.
Utilize pump 20,20, successively resultant of reaction is directed into the reactor drum 10,10 of secondary segment.In reactor drum 10, utilize condensing surface 12,12,12 will evaporate the composition condensation, deliver to then in the reactor drum 10,10 and mixing tank 14 of secondary segment.The part of uncooled a small amount of resultant of reaction is delivered to cooling tower 24.
Composition at the bottom of the tower of the reactor drum 10 of terminal section is delivered to hydrogenchloride to be removed in the tower 22; The cat head of removing tower 22 through lower heating from hydrogenchloride with hydrogenchloride with separate with hydrocarbon compound that it accompanies; It is delivered to cooling tower 24, in this cooling tower, utilize pump 28 to carry out the refrigerative water-phase component and intersperse among in the tower and cool off through accessory condensing surface 26; Thereby in cooling tower 24, separate into water and hydrocarbon compound, obtain the 35%HCl aqueous solution with the mode of this isolating water-phase component.Hydrocarbon compound in the settling bath 30 that accumulates in the bottom at the bottom of the tower of being located at cooling tower 24 utilizes the knockout tower (not shown) of back segment to separate into water and hydrocarbon compound, and hydrocarbon compound is utilized again.
Resultant of reaction for accumulating at the bottom of hydrogenchloride is removed the tower of tower 22 can use the proper process means afterwards, Yi Bian remove TCB, m-DCB, o-DCB, Yi Bian target p-DCB crystallization is separated out, carries out commercialization.In addition, symbol 32 is a drawdown pump.
(the 2nd embodiment)
Fig. 9 representes the 2nd embodiment of the present invention.
Make in the method for santochlor in that benzene is carried out chlorination as prepared using chlorine, compare with the speed of response of benzene and chlorine, as the speed of response slow (Figure 12) of the monochloro-benzene and the chlorine of reaction intermediates, big thereby needed catalytic amount relatively becomes.Therefore, it is big that the reactor drum of catalyst filling becomes, and facility investment simultaneously increases.
Therefore, the 2nd embodiment has carried out novel motion for the supply method of chlorine.Be the method for manufacture of following santochlor specifically: said reactor drum has multistage; The unreacted chlorine of said raw material, heat-eliminating medium, chlorine and/or back segment is supplied in the reactor drum of first section; The resultant of reaction of leading portion is supplied in the reactor drum of secondary segment; The chlorine of heat-eliminating medium and excess quantity is supplied in the later reactor drum of secondary segment; Formation reaction thing by terminal section obtains the bullion santochlor.Can improve the speed of response (Figure 12) of monochloro-benzene and chlorine through this method.
In addition, if the chlorine of excess supply amount, then under situation, contain the dichlorobenzene and the chlorine reaction of excess quantity, the generation trichloro-benzene as the santochlor of target resultant as the homogeneous catalyst of prior art; But in the present invention,, can suppress the generation of trichloro-benzene through using zeolite catalyst.Shown in figure 13, even at Cl
2Carry out the manufacturing of santochlor under the condition more than the/MCB=1.0, the chlorination degree of resultant of reaction also stops near 2.0, has suppressed the trichloro-benzene building-up reactions.
The reactor drum 10 of Fig. 9 is 3 sections formations.For benzene 1, utilize the not shown moisture means of removing in advance moisture to be removed the back as required and supply with from the cat head of the 1st section reactor drum 10 as raw material.
Utilize pump 20,20, successively resultant of reaction is directed into the reactor drum 10,10 of secondary segment.In reactor drum 10, utilize condensing surface 12,12,12 will evaporate composition (being mainly heat-eliminating medium) condensation, deliver to the reactor drum 10,10 and the mixing tank 14 of secondary segment then.For unreacted chlorine in the reactor drum 10 and/or the hydrogenchloride that generates by reaction, supply with from the cat head of the reactor drum 10 of leading portion.A part and the chloroform of uncooled a small amount of resultant of reaction are supplied in the cooling tower 24.
For composition at the bottom of the tower of the reactor drum 10 of terminal section and deliver to the uncooled resultant of reaction and the chloroform of cooling tower 24, flow process thereafter is identical with the 1st embodiment.
(the 3rd embodiment)
Figure 10 representes the 3rd embodiment of the present invention.
The 3rd embodiment has carried out novel motion for the method to each section base feed.Be following santochlor method of manufacture specifically: said reactor drum has multistage; Said raw material, chlorine and/or heat-eliminating medium are supplied in the reactor drum of first section; The resultant of reaction of leading portion is separated into unreacting material and resultant, unreacting material is returned in the reactor drum of leading portion, resultant is supplied in the reactor drum of secondary segment; Chlorine and heat-eliminating medium are supplied in the later reactor drum of secondary segment; Resultant of reaction by terminal section obtains santochlor.
Compare with the method that first section resultant of reaction separates in the reactor drum that just is supplied to secondary segment, can improve the para-selectivity (Figure 14) in the resultant of reaction through this method.
The reactor drum 10 of Figure 10 is 2 sections formations.For benzene 1, utilize the not shown moisture means of removing in advance moisture to be removed the back as required and supply with from the cat head of the 1st section reactor drum 10 as raw material.
For chlorine 2, in the reactor drum 10,10 of each section, supply with from its cat head with mode arranged side by side.In each reactor drum 10,10, set up condensing surface 12,12.Chloroform (heat-eliminating medium) 3 delivered to mixing tank 14 by storage tank, be supplied to by its cat head through pump 16 in the 1st section the reactor drum 10.In addition, recovery chloroform 3A that the back operation of utilizing the not shown treatment scheme of detailed content is reclaimed and benzene 1 are together supplied with from the cat head of the 1st section reactor drum 10.In addition, the recovery chloroform 3B that the back operation of likewise utilizing the not shown treatment scheme of detailed content is reclaimed is supplied in the said mixing tank 14.
Utilize pump 20,20, successively resultant of reaction is directed into unreacting substance knockout tower 13,13.In reactor drum 10, utilize condensing surface 12,12 will evaporate composition (being mainly heat-eliminating medium) condensation, deliver to then in the reactor drum 10 and mixing tank 14 of secondary segment.A part and the chloroform of uncooled a small amount of resultant of reaction are delivered to cooling tower 24.
In unreacting substance knockout tower 13, through lower heating with the unreacting substance of leading portion with separate with the tower portion of its hydrogenchloride that accompanies by unreacting substance knockout tower 13.Further utilize condensing surface 15 to make the evaporation composition condensation in the unreacting substance knockout tower 13, then unreacting substance is returned in the reactor drum 10 of leading portion.The uncooled hydrogenchloride and the part of a small amount of unreacting substance are delivered to cooling tower 24.
In cooling tower 24, utilize pump 28 to carry out the refrigerative water-phase component and intersperse among in the tower and cool off through accessory condensing surface 26, in cooling tower 24, separate into water and chloroform thus mutually, and obtain the 35%HCl aqueous solution with the mode of this isolating water-phase component.For the chloroform phase in the settling bath 30 that accumulates in the bottom at the bottom of the tower of being located at cooling tower 24, the knockout tower (not shown) through back segment separates into water and chloroform, and chloroform is utilized again.
Heat-eliminating medium for the terminal section that comes autoreactor 10 can utilize condensing surface 12 that it is cooled off, and is directed into mixing tank 14 then, uses it for the supply of new chloroform and uses.
For the resultant of reaction at the bottom of the tower of the unreacting substance knockout tower 13 that accumulates in terminal section, target p-DCB crystallization is separated out carry out commercialization while can use the proper process means to remove TCB, m-DCB, o-DCB afterwards.
(the 4th embodiment)
Figure 11 representes the 4th embodiment of the present invention.
Utilize pump 20,20,20 successively resultant of reaction to be directed into separator 19,19, 19.In separator 19,19,19, resultant of reaction is separated with aluminium oxide catalyst, the aluminium oxide catalyst after separating is returned in the reactor drum 10,10,10 of leading portion.Removing tower 22 to the reactor drum 10,10 of secondary segment and hydrogenchloride supplies with and has carried out the isolating resultant of reaction of aluminium oxide catalyst.Reactor drum 10,10 or cooling tower 24 to secondary segment are carried the hydrogen chloride gas that is produced in each reactor drum 10,10,10.
Remove in the tower 22 at hydrogenchloride; Through lower heating with hydrogenchloride with separate with cat head that its hydrocarbon compound that accompanies is removed tower 22 from hydrogenchloride; It is delivered in the cooling tower 24, in this cooling tower 24, utilize pump 28 to carry out the refrigerative water-phase component and intersperse among in the tower and cool off through accessory condensing surface 26; In cooling tower 24, separate into water and hydrocarbon compound thus, obtain the 35%HCl aqueous solution with the mode of this isolating water-phase component.For the hydrocarbon compound of the settling bath 30 that accumulates in the bottom at the bottom of the tower of being located at cooling tower 24, the knockout tower (not shown) through back segment separates into water and hydrocarbon compound, and hydrocarbon compound is utilized again.
For the resultant of reaction that accumulates at the bottom of hydrogenchloride is removed the tower of tower 22, target p-DCB crystallization is separated out carry out commercialization while can use the proper process means to remove TCB, m-DCB, o-DCB afterwards.
Embodiment
(embodiment 1)
According to the flow process of Fig. 1, as raw material, utilize chlorine to carry out chlorination benzene, make santochlor.In reactor drum, the aluminum oxide formed body of BEA zeolite is housed in the mode with fixed bed.
In temperature of reaction is that 75 ℃, pressure are 1.8kg/cm
2Condition under carry out chlorination reaction.Be about 2.0 as chlorination degree.
The selectivity of the p-DCB that obtains is 77.7%, has stably made p-DCB with highly selective.
(embodiment 2)
According to the flow process of Fig. 9, as raw material, utilize chlorine to carry out chlorination benzene, make santochlor.In reactor drum, the silicon-dioxide formed body of BEA zeolite catalyst is housed in the mode with fixed bed.
In temperature of reaction is that 80 ℃, pressure are 1.8kg/cm
2Condition under carry out chlorination reaction.Be about 2.0 as chlorination degree.
The selectivity of the p-DCB that obtains is 74.6%, has stably made p-DCB with highly selective.
(embodiment 3)
According to the flow process of Figure 10, as raw material, utilize chlorine to carry out chlorination benzene, make santochlor.In reactor drum, the silicon-dioxide formed body of BEA zeolite catalyst is housed in the mode with fixed bed.
In temperature of reaction is that 80 ℃, pressure are 1.8kg/cm
2Condition under, carry out chlorination reaction.Be about 2.0 as chlorination degree.
The selectivity of the p-DCB that obtains is 74.6%, has stably made p-DCB with highly selective.
(embodiment 4)
According to the flow process of Figure 11, as raw material, utilize chlorine to carry out chlorination benzene, make santochlor.In reactor drum, the granulation that the BEA zeolite catalyst is housed in the mode with slurry attitude bed is the silicon-dioxide formed body of 0.8～3.2mm.
In temperature of reaction is that 80 ℃, pressure are 1.8kg/cm
2Condition under carry out chlorination reaction.Be about 2.0 as chlorination degree.
The selectivity of the p-DCB that obtains is 72.5%, has stably made p-DCB with highly selective.
(comparative example)
Homogeneous catalyst iron(ic)chloride FeCl has been shown as the use of existing method
3Comparative example.Shown in figure 15; As reaction unit, use the complete hybrid reactor 50 that possesses chuck 51 and stirrer 52, by supplying with fan chlorine is supplied to wherein; Benzene and iron(ic)chloride also are supplied to wherein, react while utilize water coolant unit 53 to cool off through chuck 51.The resultant of reaction that comes from the bottom is stockpiling after the cooling in reservoir 54; The gas-liquid composition that comes from the top is stockpiling after the cooling in reservoir 55.
Reaction conditions is described below.
Zero catalyst Fe Cl
3Concentration: 0.0088 catalyzer mol/ benzene mol
Zero raw material chlorine feed speed: 0.85mol/ benzene mol
Zero temperature of reaction: 80 ℃
The chlorating resultant of being represented the benzene in this reaction process by reaction degree of carrying out (chlorination degree) changes, and obtains Figure 16 thus.
Can know that by Figure 16 the reaction of homogeneous catalyst is progressively to carry out with parallel mode.As its reason, because homogeneous catalyst not have the resistance that spreads, so benzene and monomer or monomer and disome react simultaneously according to thinking.Therefore, the disome selectivity maximum in the reaction rests on 80%.
The optionally variation that is accompanied by the PDCB among the DCB productive rate DCB is shown in Figure 17; The passing that is accompanied by chlorination PDCB productive rate is shown in Figure 18.Because it is sterically hindered that homogeneous catalyst does not have in ortho position-para-orientation, therefore shown in figure 17, contraposition body selectivity is 60%, is lower value.In addition, shown in figure 18, because disome selectivity maximum rests on 80%, therefore the contraposition body maximum yield in the reaction is 50%.
Temperature is dropped to 70 ℃ for 80 ℃ from the temperature of reaction of standard conditions to experimentize.The result is shown in Figure 19.Even can know and reduce temperature of reaction, contraposition body selectivity does not change yet.
Then, catalytic amount is reduced to about 1/20 0.0010g-cat/g-Bz (0.00049 catalyzer mol/ benzene mol) from 0.0181g-cat/g-Bz (0.0088 catalyzer mol/ benzene mol), the result can know active not variation; Shown in figure 20, can be organized into a curve, selectivity does not change yet.
As stated, can know, just can't make p-DCB with highly selective as long as use homogeneous catalyst.
Industrial utilization property
According to the present invention, can obtain continuously as the extremely high compound of the commercial value of PPS raw material.
Nomenclature
1 ... Benzene, 2 ... Chlorine, 10 ... Reactor drum, 11 ... Chuck, 12 ... Condensing surface, 18 ... Zeolite catalyst, 20 ... Pump, 22 ... Hydrogenchloride is removed tower, 24 ... Cooling tower, 26 ... Condensing surface, 28 ... Pump, 30 ... Settling bath, 32 ... Drawdown pump.
Claims (15)
1. the method for manufacture of a santochlor; It is as raw material and use chlorine to carry out the method that santochlor is made in chlorination with benzene and monochloro-benzene at least a; This method of manufacture is characterised in that; Above-mentioned raw materials and above-mentioned chlorine are directed in the reactor drum that the catalyzer that contains zeolite is housed in the mode with fixed bed, and the moulding base that above-mentioned catalyzer utilization is principal constituent with the alumina sol carries out moulding to zeolite and obtains.
2. the method for manufacture of a santochlor; It is as raw material and use chlorine to carry out the method that santochlor is made in chlorination with benzene and monochloro-benzene at least a; This method of manufacture is characterised in that; In the interior reactor drum that the catalyzer that contains zeolite is housed, the unreacted chlorine of above-mentioned raw materials, chlorine and/or back segment is supplied in the reactor drum of first section with multistage; The resultant of reaction of leading portion is supplied in the reactor drum of secondary segment; The chlorine of excess quantity is supplied in the later reactor drum of secondary segment; Formation reaction thing by terminal section obtains santochlor.
3. the method for manufacture of a santochlor; It is as raw material and use chlorine to carry out the method that santochlor is made in chlorination with benzene and monochloro-benzene at least a; This method of manufacture is characterised in that; In the interior reactor drum that the catalyzer that contains zeolite is housed, above-mentioned raw materials, chlorine are supplied in the reactor drum of first section with multistage; The resultant of reaction of leading portion is separated into unreacting material and resultant, unreacting material is returned in the reactor drum of leading portion, resultant is supplied in the reactor drum of secondary segment; Chlorine is supplied in the later reactor drum of secondary segment; Resultant of reaction by terminal section obtains santochlor.
4. the method for manufacture of a santochlor; It is as raw material and use chlorine to carry out the method that santochlor is made in chlorination with benzene and monochloro-benzene at least a; This method of manufacture is characterised in that, above-mentioned raw materials and above-mentioned chlorine are directed into to be equipped with in the reactor drum of the catalyzer that contains zeolite in the mode of starching the attitude bed.
5. the method for manufacture of each described santochlor of claim 1～3 wherein, is directed into each section of said reactor drum with at least a heat-eliminating medium of methyl chloride and monochloroethane, makes above-mentioned heat-eliminating medium evaporation, and the temperature that suppresses said chlorination reaction rises.
6. the method for manufacture of the described santochlor of claim 5, wherein, the vaporised gas composition of said heat-eliminating medium utilizes this phlegma as said heat-eliminating medium in the reactor drum condensed exterior again.
7. the method for manufacture of claim 2 or 3 described santochlor, wherein, with being loaded in the said reactor drum in the said mode of catalyzer that contains zeolite with fixed bed.
8. the method for manufacture of each described santochlor of claim 2～4, wherein, it is that the moulding base of principal constituent carries out moulding to zeolite and obtains that the said catalyzer that contains zeolite utilizes with the alumina sol.
9. the method for manufacture of each described santochlor of claim 1～4, wherein, said zeolite is the proton type zeolite.
10. the method for manufacture of each described santochlor of claim 1～4, wherein, said zeolite is a zeolite beta.
11. the method for manufacture of each described santochlor of claim 1～4, wherein, said zeolite is a MFI type zeolite.
12. the method for manufacture of each described santochlor of claim 1～3 wherein, is utilized to fall to flow to make said raw material and chlorine circulation.
13. the method for manufacture of each described santochlor of claim 1～4, wherein, said chlorination reaction is that 40～130 ℃, pressure are to carry out below the 10atm in temperature.
14. the method for manufacture of the described santochlor of claim 1, wherein, said reactor drum has multistage; Chlorine is supplied in each reactor drum with mode arranged side by side; Said raw material and chlorine are supplied in the reactor drum of first section; The resultant of reaction of leading portion is supplied in the reactor drum of secondary segment; Chlorine is supplied in the later reactor drum of secondary segment with mode arranged side by side; Resultant of reaction by terminal section obtains santochlor.
15. the method for manufacture of the described santochlor of claim 4, wherein, said reactor drum has multistage; Said raw material, chlorine are supplied in the reactor drum of first section; The resultant of reaction of leading portion is supplied in the reactor drum of secondary segment; Chlorine is supplied in the later reactor drum of secondary segment with mode arranged side by side; Resultant of reaction by terminal section obtains santochlor.
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| JP2009-077003 | 2009-03-26 | ||
| JP2009-077002 | 2009-03-26 | ||
| JP2009-077004 | 2009-03-26 | ||
| JP2009-077001 | 2009-03-26 | ||
| JP2009077001A JP5425503B2 (en) | 2009-03-26 | 2009-03-26 | Method for producing paradichlorobenzene |
| JP2009077003A JP5366610B2 (en) | 2009-03-26 | 2009-03-26 | Method for producing paradichlorobenzene |
| JP2009077004A JP5669362B2 (en) | 2009-03-26 | 2009-03-26 | Method for producing paradichlorobenzene |
| JP2009077002A JP5474389B2 (en) | 2009-03-26 | 2009-03-26 | Method for producing paradichlorobenzene |
| PCT/JP2010/054647 WO2010110163A1 (en) | 2009-03-26 | 2010-03-18 | Process for production of p-dichlorobenzene |
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| CN109574789A (en) * | 2018-11-14 | 2019-04-05 | 江苏隆昌化工有限公司 | A kind of method of Benzene Chloride oriented chlorination production paracide |
| CN109574789B (en) * | 2018-11-14 | 2021-12-14 | 江苏隆昌化工有限公司 | Method for producing p-dichlorobenzene by directional chlorination of chlorobenzene |
| EP4365158A1 (en) | 2022-11-04 | 2024-05-08 | PCC ROKITA Spolka Akcyjna | Method of selective paradichlorobenzene preparation with improved catalytic system recovery |
Also Published As
| Publication number | Publication date |
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| TWI535683B (en) | 2016-06-01 |
| TW201035007A (en) | 2010-10-01 |
| CN102361841B (en) | 2014-04-09 |
| WO2010110163A1 (en) | 2010-09-30 |
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