CN102361841B - Process for production of p-dichlorobenzene - Google Patents
Process for production of p-dichlorobenzene Download PDFInfo
- Publication number
- CN102361841B CN102361841B CN201080013416.7A CN201080013416A CN102361841B CN 102361841 B CN102361841 B CN 102361841B CN 201080013416 A CN201080013416 A CN 201080013416A CN 102361841 B CN102361841 B CN 102361841B
- Authority
- CN
- China
- Prior art keywords
- reactor
- santochlor
- chlorine
- zeolite
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
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 manufacture method of santochlor, particularly relate to using benzene (being also expressed as below " Bz ") and monochloro-benzene (being also expressed as below " MCB ") at least one party as raw material, using zeolite as catalyzer, utilize chlorine to carry out the method that santochlor (being also expressed as below " p-DCB " or " PDCB ") manufactured in chlorination.In addition, in this manual, " zeolite catalyst " expression " containing the catalyzer of zeolite ".
Background technology
P-DCB is as the raw material of medicine, agricultural chemicals; And himself is as sterilant, insect-proof agent; The raw material that is further used as polyphenylene sulfide (PPS) is the high compound of industrial value.
In the past, for p-DCB, known had using Lewis acids such as iron(ic) chloride, antimony pentachlorides as catalyzer a manufacture method of benzene and/or monochloro-benzene being carried out to liquid phase chlorination.The activity of iron(ic) chloride is high, and chlorine transformation efficiency reaches more than 99.99%, and the unreacted chlorine in by-product salt acid gas is the residual degree of denier.But the selection rate for the para-orientation thing as target compound, mostly is 60% left and right most while using catalyzer separately, adds promotor and can be increased to 75% left and right.
In recent years, as take selection rate, as more than 90.4% (904%) mode, manufacture the method for p-DCB, as shown in patent documentation 1, patent documentation 2 etc., disclose and used zeolite L as the method for catalyzer.But, use zeolite as the method for catalyzer, to be the method for laboratory level, it is believed that it is not the concrete grammar that can be used as the degree of actual device running.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Publication 63-12450 communique
Patent documentation 2: TOHKEMY 2001-213815 communique
Non-patent literature
Non-patent literature 1: shallow Gang Zuo knows husband < < Na ノ Port one ラ ス ゼ ォ ラ ィ ト catalyst table face Let Meter と Tone System method (nanoporous zeolite catalyst surface design and preparation method) > >, Chemical Engineering, in April, 2008 number, 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 manufacturing p-DCB (santochlor), in the situation that turning round as actual device, can obtain target compound with high yield, and can steady running.
By following explanation, can recognize other problems.
For the method for dealing with problems
The present invention who has solved this problem is as described below.
[invention claimed in claim 1]
A kind of manufacture method of santochlor, it is to using at least one of benzene and monochloro-benzene to carry out as raw material and with chlorine the method that santochlor is manufactured in chlorination, this manufacture method is characterised in that, above-mentioned raw materials and above-mentioned chlorine are directed in the reactor being equipped with in the mode with fixed bed containing the catalyzer of zeolite, above-mentioned catalyzer is to utilize to take moulding base that alumina sol is principal constituent and zeolite is carried out to moulding obtain.
[invention claimed in claim 2]
A kind of manufacture method of santochlor, it is to using at least one of benzene and monochloro-benzene to carry out as raw material and with chlorine the method that santochlor is manufactured in chlorination, this manufacture method is characterised in that, in the interior reactor with multistage being equipped with containing the catalyzer of zeolite, the unreacted chlorine of above-mentioned raw materials, chlorine and/or back segment is supplied in the reactor of first section; The resultant of reaction of leading portion is supplied in the reactor of secondary segment; The chlorine of excess quantity is supplied in the later reactor of secondary segment; Formation reaction thing by terminal section obtains santochlor.
[invention claimed in claim 3]
A kind of manufacture method of santochlor, it is to using at least one of benzene and monochloro-benzene to carry out as raw material and with chlorine the method that santochlor is manufactured in chlorination, this manufacture method is characterised in that, in the interior reactor with multistage being equipped with containing the catalyzer of zeolite, above-mentioned raw materials, chlorine are supplied in the reactor of first section; The resultant of reaction of leading portion is separated into unreacting material and resultant, unreacting material is returned in the reactor of leading portion, resultant is supplied in the reactor of secondary segment; Chlorine is supplied in the later reactor of secondary segment; Resultant of reaction by terminal section obtains santochlor.
[invention claimed in claim 4]
A kind of manufacture method of santochlor, it is to using at least one of benzene and monochloro-benzene to carry out as raw material and with chlorine the method that santochlor is manufactured in chlorination, this manufacture method is characterised in that, above-mentioned raw materials and above-mentioned chlorine is directed into starch in the reactor being equipped with in the mode of state bed containing the catalyzer of zeolite.
[invention claimed in claim 5]
The manufacture method of the santochlor described in claim 1～3 any one, wherein, is directed at least one heat-eliminating medium of methyl chloride and monochloroethane in each section of described reactor, makes the temperature that described heat-eliminating medium evaporates, suppresses described chlorination reaction increase.
[invention claimed in claim 6]
The manufacture method of santochlor claimed in claim 5, wherein, the vaporised gas composition of described heat-eliminating medium, in reactor condensed exterior, recycles this phlegma as described heat-eliminating medium.
[invention claimed in claim 7]
The manufacture method of the santochlor described in claim 2 or 3, wherein, is loaded in described reactor in the mode by the described catalyzer containing zeolite with fixed bed.
[invention claimed in claim 8]
The manufacture method of the santochlor described in claim 2～4 any one, wherein, the described catalyzer containing zeolite is to utilize to take moulding base that alumina sol is principal constituent and zeolite is carried out to moulding obtain.
[invention claimed in claim 9]
The manufacture method of the santochlor described in claim 1～4 any one, wherein, described zeolite is proton type zeolite.
[invention claimed in claim 10]
The manufacture method of the santochlor described in claim 1～4 any one, wherein, described zeolite is zeolite beta.
[invention described in claim 11]
The manufacture method of the santochlor described in claim 1～4 any one, wherein, described zeolite is MFI type zeolite.
[invention described in claim 12]
The manufacture method of the santochlor described in claim 1～3 any one, wherein, stream falls in utilization makes described raw material and chlorine circulation.
[invention described in claim 13]
The manufacture method of the santochlor described in claim 1～4 any one, wherein, described chlorination reaction is that 40～130 ℃, pressure are to carry out below 10atm in temperature.
[invention described in claim 14]
The manufacture method of santochlor claimed in claim 1, wherein, described reactor has multistage; Chlorine is supplied in each reactor in mode arranged side by side; Described raw material and chlorine are supplied in the reactor of first section; The resultant of reaction of leading portion is supplied in the reactor of secondary segment; Chlorine is supplied in the later reactor of secondary segment in mode arranged side by side; Resultant of reaction by terminal section obtains santochlor.
[invention described in claim 15]
The manufacture method of santochlor claimed in claim 4, wherein, described reactor has multistage; Described raw material, chlorine are supplied in the reactor of first section; The resultant of reaction of leading portion is supplied in the reactor of secondary segment; Chlorine is supplied in the later reactor of secondary segment in mode arranged side by side; Resultant of reaction by terminal section obtains santochlor.
Invention effect
According to the present invention, can eliminate the shortcoming as the device that selectivity is low, separation and recovery of catalyst the is related burden of the p-DCB in the homogeneous catalysts such as iron(ic) chloride of prior art, can steady running while turning round as actual device.
Accompanying drawing explanation
Fig. 1 is the schema of the 1st embodiment of the present invention.
Fig. 2 is the schema of base feed, chlorine under upwelling condition.
Fig. 3 means in the situation that used and using respectively silicon dioxide gel, alumina sol as the BEA of moulding base, the graphic representation of DCB productive rate, para-selectivity.
Fig. 4 means in the situation that having used silica-alumina catalyzer, the graphic representation of DCB productive rate, para-selectivity.
Fig. 5 means in the situation that used respectively and using alumina sol as BEA, MFI, the USY of moulding base, the graphic representation of DCB productive rate, para-selectivity.
Fig. 6 means that the metallic cation replacement rate along with the ion-exchange point of zeolite catalyst changes, the graphic representation of the variation of DCB productive rate, para-selectivity.
Fig. 7 is the graphic representation that has used the reaction in the situation of zeolite catalyst to carry out.
It is that 80 ℃, liquid phase cools temperature are under the condition of 58 ℃ that Fig. 8 means in temperature of reaction, is represented the explanation graphic representation of rate of recovery etc. by the relation of the ratio of pressure and chloroform/benzene.
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 embodiments of the present invention and do not carry out the comparative graph of the para-selectivity under the separated condition of resultant of reaction.
Figure 15 is the summary pie graph of the reaction unit of conventional example (comparative example: use homogeneous catalyst).
Figure 16 is the composition history curve figure of each material in conventional example (use homogeneous catalyst).
Figure 17 is the optionally graphic representation of the p-DCB in conventional example (use homogeneous catalyst).
Figure 18 is the graphic representation that is accompanied by chlorination p-DCB productive rate in conventional example (use homogeneous catalyst).
Figure 19 means in conventional example (use homogeneous catalyst) that temperature of reaction is on the graphic representation optionally affecting.
Figure 20 means in conventional example (use homogeneous catalyst) that catalytic amount is on the graphic representation optionally affecting.
Embodiment
(basic conception of invention)
As mentioned above, while using the homogeneous catalysts such as iron(ic) chloride, not only p-DCB selectivity is low, and the burden of the separating and reclaiming device of catalyzer also can become large.In the present invention, by using zeolite catalyst, can improve the selectivity of p-DCB, and, by using solid catalyst, catalyzer can be recycled.
In addition, as mentioned above, chlorination reaction is fierce thermopositive reaction.By the way,, if do not dispel the heat, can be warming up to simply 400～500 ℃.Therefore, need to suppress rightly temperature and rise, in certain temperature range, keep on the go.If temperature is too low, can cause that viscosity uprises, the pressure-losses increases.On the contrary, the in the situation that of high temperature, chlorine is dissolved into as speed limit (rule speed), makes to react 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 reaction pressure to determine and be maintained suitable temperature of reaction (speed of response).
As the method that suppresses thermopositive reaction, it is believed that in the reactors such as chuck and coil pipe, arrange cooling end method, by the solvent with a large amount of, suppress method that temperature rises (as candidate's solvent, think and have 1,2-ethylene dichloride or MCB) and by and the method for carrying out with cooling end and solvent etc., certainly also can use these methods.Yet, although be gas-liquid mixed phase state under preferred reaction conditions (40～130 ℃, below 10atm), but the whole heat transfer rate for reacting part-metal portion-cooling end, owing to comparing air phase volume with liquid phase volume, there is overwhelming advantage, therefore the heat transfer rate of reacting part becomes mastery factor, and overall heat transfer coefficient is only 10～30kcal/m
2hr ℃ of left and right, under this condition, needs huge heat transfer area, as reactor, is difficult to specialize.
Therefore, in the present invention, proposed to utilize the direct cooling mode of vaporization heat of cooling solvent as preferred condition.It is present in and reacts in system by making to have with the compound of the boiling point of reaction conditions same degree, makes the vaporization heat accompanying with this compound evaporation be transferred to this compound, can absorb thus produced huge reaction heat.
The compound of evaporation can recycle by condensation, during condensation, can use and can guarantee that overall heat transfer coefficient is 600～1100kcal/m
2the general external heat exchangers such as the shell-tube type of hr ℃ (shell and tube).
For the compound that can use in this direct heat-eliminating medium, take and do not react as condition, the compound that is suitable for the synthetic chlorination reaction of p-DCB 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, chloromethane alkanes, the chloroethene alkanes such as 1,1-trichloroethane (73.9 ℃ of Tb).Thereby can consider to select applicable pressure condition to the boiling point of desired temperature of reaction and benzene and direct heat-eliminating medium and carry out stable temperature treatment.
In the operation of following explanation, enumerated and adopted the example of the trichloromethane (another name chloroform) of the atmospheric boiling point with 61 ℃ to describe, but also can use above-mentioned other chloromethane alkanes or chloroethene alkanes, confirm that in addition these compounds also can be used two or more.
In addition, the present invention uses benzene and/or chlorobenzene and chlorine, uses above-mentioned direct heat-eliminating medium (being chloroform in following example) simultaneously.It is arranged, as 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
Above composition is considered, suitable separation means is combined, obtain target santochlor.
If the example to reaction formula represents, as 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 the example as the not chlorine addition reaction of preferred side reaction is represented, as described below.
The tetrachloro tetrahydrobenzene of the chlorine addition reaction based on 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 the tetrachloro tetrahydrobenzene that not preferred side reaction generates and lindane likely become catalyzer, worries that it may cause the deteriorated of catalyzer.
Think in addition, in this reaction, the moisture of trace is necessary for showing ionic reaction in zeolite catalyst.But necessary above moisture can cause the corrosion of device, and can relate to reaction, likely reduce reactivity and generate by product.Therefore, expectation is suitably adjusted the moisture in raw material.
(optimal way of zeolite catalyst)
In the present invention, use the catalyzer containing 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 large fine pore type, mordenite (MOR), X-type, T-shaped (FAU) etc., these zeolites all can be used.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-shaped (FAU), the Y type (USY) of large fine pore type.
When zeolite is monomer, it cannot moulding, becomes diameter
small powder.While using in slurry state bed, zeolite catalyst of the present invention can be used with the form of powder, and the particle that also can manufacture diameter 0.8～3.2mm is used in the mode of formed body.In addition, also can be shaped to as required the special shapes such as ring-type, four leaves (Network ヮ mono-De ロ mono-Block) shape, gilled rings shape.Use zeolite catalyst if consider after, carry out recycling, preferably in the mode of the formed body that more easily reclaims, use.As for zeolite being carried out to the moulding base material (shaping assistant) of moulding, such as the silicon-dioxide aerosol, alumina sol etc. that use nanoparticle size, particularly preferably use the alumina sol of single component (Unit body).DCB productive rate, the para-selectivity of the catalyzer obtaining using respectively alumina sol, silicon dioxide gel to carry out moulding to proton type BEA compare, result can be distinguished, although para-selectivity is not found large difference, but utilize the catalyzer through alumina sol moulding, can obtain relatively long-term and stably high yield (Fig. 3).In the prior art, the moulding of zeolite is carried out with silicon dioxide gel, due to the atopic that is difficult to form new ion-exchange point, can not hinder zeolite on zeolite surface, is therefore preferred.But in the reaction of the manner, by using alumina sol, para-selectivity can not decline, and the stability of catalyzer self improves.Therefore implied that above-mentioned reaction does not occur over just in the hole of zeolite, also has generation at the ion-exchange point that is formed at preformed catalyst surface by aluminum oxide.If reaction occurs over just in the hole of zeolite, may there is deteriorated by the catalyzer due to the obturation of hole, and if the reaction of catalyst surface is compared with the past, degradation speed also can reduce.
As mentioned above, if the aluminum oxide of zeolite surface is above-mentioned ion-exchange point, also can say the certainty of not using zeolite.But if carry out same reaction with silica-alumina catalyzer, productive rate becomes very low, demonstrate catalyst activity very low (Fig. 4).In addition, during with use zeolite, compare, para-selectivity is also lower value.Distinguish thus: in p-DCB generates, in order to make the catalyzer with aluminum oxide keep high yield, selectivity, must using special skeleton that zeolite was had as carrier.In non-patent literature 1, expressed the catalyst activity that utilizes the structure of zeolite can improve aluminum oxide.
Zeolite framework has a great difference according to the difference of zeolite type.For in zeolite as in the alumina sol preformed catalyst of the ZSM-5 (MFI) that uses typically of the zeolite of fine pore, large fine pore, β type (BEA), Y type (USY), its activity is compared, result can be distinguished, as shown in Figure 5, DCB productive rate low (because generating in a large number TCB (not shown) in side reaction) when using USY; And on the other hand, when using BEA, MFI, demonstrate high DCB productive rate.The difference that has implied the surface tissue due to skeleton structure of zeolite has caused impact to the catalyst activity of aluminum oxide.In the present invention, can say and particularly preferably use ZSM-5 (MFI), β type (BEA).
Moulding base that the aluminum oxide of take is principal constituent is selected with respect to total catalyst levels as 10 quality %～50 quality %, is preferably the amount of 15 quality %～30 quality %.If be less than 10 quality %, the associativity variation of catalyst activity step-down, and zeolite and moulding base.If more than 50 quality %, the volume of catalyzer increase to volume required more than, cannot give play to the characteristic of above-mentioned zeolite framework simultaneously, catalyst activity still can decline.
The zeolite of the zeolite catalyst of the manner is more preferably used proton type.Its reason is, if having been found that, for example uses, by metallic cation (sodium ion) the ion-exchange point of zeolite carried out to the zeolite replacing, although initial activity improves, and catalyst activity can decline rapidly at short notice (not shown).
(other modes of zeolite catalyst)
Following discloses there is no to use a zeolite catalyst take in the example of the moulding base that aluminum oxide is principal constituent.In the manner, use the zeolite that has been replaced ion-exchange point by metallic cation.
In the manner with at least a portion of the ion-exchange point of zeolite by metallic cation, preferably used by the occupied state of sodium cation.Particularly in the situation that take the more than at least 10% of ion-exchange point, preferably 10%～85% occupied by above-mentioned metallic cation of zeolite of the preformed catalyst that zeolite is principal constituent, effect large (Fig. 6).If the occupied ratio of above-mentioned metallic cation is less than 10%, can produce the Efficiency Decreasing of above-mentioned chlorination reaction or side reaction increase etc.
In order to make at least a portion of ion-exchange point of zeolite in by metallic cation, particularly by the occupied state of sodium cation, can utilize known method to carry out ion-exchange and use.For ion-exchange is sodium cation, generally by the aqueous solution with sodium salt, preferably with sodium chloride aqueous solution, carry out 2 exchange operations above and carry out.
And distinguish, the in the situation that of the homogeneous catalysts such as iron(ic) chloride, reaction is not only carried out in mode progressively, also in the mode walking abreast, carries out; And on the other hand, for zeolite catalyst, reaction almost 100% is carried out (Fig. 7) in mode progressively.It is believed that this is due to the homogeneous catalyst in the situation that, in the stage that remains benzene, as the monomer of resultant or disome and benzene similarly arbitrarily with catalyzer formation complex compound and react; And in contrast, owing to there being the resistance of the diffusion of reaction molecular in zeolite catalyst, therefore think to react according to benzene, monomer, disome, trisome, this order easily spreading of limbs and progressively carry out.
To take respectively the preformed catalyst that these 2 kinds of zeolites are principal constituent, compare, result is known, and the performance of the catalyzer that ZSM-5 (MFI) zeolite of take is principal constituent exists in circulation system cannot give full play to such problem points, and zeolite beta is more excellent.
For for improving the resistance of the diffusion of the zeolite catalyst that selectivity selects, in require can to stablize the circulation system of use in the interior reactor that preformed catalyst is housed, can cause active remarkable reduction.In addition, for take the result of flow type of reactor of the preformed catalyst that zeolite beta is principal constituent based on interior being equipped with, known with based on the step result of the slurry reactor of preformed catalyst powdered is compared, be that activity or selectivity are all more excellent.
For the interior zeolite beta of take the preformed catalyst that zeolite is main component being loaded in reactor, its SiO
2/ Al
2o
3ratio be preferably 14～100 (more preferably 16～50).It is believed that, if be less than 14, the outer surface part at crystallization of zeolites or particle has octahedral aluminium, it is separately or by the interaction with being present in the functional group of 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 forms metal (sodium) cationic ion exchange spot or carry out chlorine addition reaction, therefore not preferred.In addition, if be greater than 100, the concentration of the active site in the pore of zeolite reduces, diffusion length is elongated, till causing thus reaction to proceed to trisome, and because the delay of resultant makes the pore internal diffusion of raw molecule be subject to resistance, thereby hindered the carrying out of goal response.
In addition, in order to make at short notice ion-exchange proceed to targeted degree, Yi Bian preferably on one side the aqueous solution of sodium salt is exchanged and carries out above exchange operations 2 times.Further, in operation, select to make the pH of solution side finish accompanying sodium-chlor to be cleaned, remove the method for carrying out in acidic side the last time simultaneously.For the concentration of aqueous solution of sodium-chlor or the number of times of amount and exchange operations now, can suitably select.
Yet, it is believed that, make at least a portion in the ion-exchange point of zeolite in being to utilize sodium-chlor to carry out the point that ion-exchange becomes sodium cation by the occupied state of sodium cation.As such site, when proton type, be considered to demonstrate highly acid Bronsted acid.
By the way, in order to make the state of zeolite of the zeolite catalyst of the manner, the preformed catalyst that is principal constituent by zeolite or the zeolite of take is made into proton type, then utilize the strong acid salt of metal, particularly sodium to carry out ion-exchange, make the more than at least 10% occupied by sodium cation of ion-exchange point, it is effective being made into such state.
In addition, in order to make the zeolite catalyst of the manner, preferably can not form with zeolite the matrix (matrix) of new ion-exchange point.As this preferred matrix, can use separately silicon-dioxide aerosol such as nanoparticle size etc.If use moulding base of more than two kinds simultaneously, can obtain new ion-exchange point at zeolite surface, likely catalyst activity is caused to detrimentally affect.In addition, because zeolite is mainly by SiO
2form, therefore preferably use SiO
2as shaping assistant.Also can by acid treatment, remove the Al of zeolite surface, then use SiO
2as shaping assistant.
As the effect of shaping assistant, must be supplied in formed body not damage the mode of the catalyst performance of zeolite, and to have can industrial use intensity.As the amount of this moulding base, select 10 quality %～50 quality %, the preferred amount of 15 quality %～35 quality %.If be less than 10 quality %, the associativity variation of zeolite and moulding base.If more than 50 quality %, the volume of catalyzer increase to volume required more than, be simultaneously easily subject to reaction raw materials and be difficult to arrive the impact of putting this diffusion to zeolite activity.
(summary of reaction unit)
In the present invention, in zeolite catalyst, be loaded in reactor.Owing to there being the deteriorated of zeolite catalyst, therefore expectation reactor is set to multistage (minimum 2 sections) and exchanges use.Zeolite catalyst can be used in the mode of fixed bed, makes raw material and chlorine circulation, also can use (Figure 11) in the mode of slurry state bed in addition.By using zeolite catalyst in the mode of slurry state bed, can effectively suppress temperature and rise, and can in certain temperature range, keep on the go.
In the mode of fixed bed, use in the situation of catalyzer, although also can utilize upwelling to make described raw material, chlorine circulation (Fig. 2), more preferably adopt the circulation (Fig. 1) of falling stream.If utilize upwelling to circulate, owing to being the external phase of liquid in reactor, therefore leave chlorine and occur the problem that backmixing is such to being dissolved in solution for resultant of reaction in speed limit or liquid, if but undertaken by falling stream, in reactor, become the external phase of gas, thereby can solve described problem.
Now, dispersion and the liquid phase Uniform Flow as the gas phase at chlorine center guaranteed in expectation, gets rid of backmixing.The flow pattern of gas-liquid mixed phase stream can change because of adopted reactor footpath.The flow pattern adopting is pulsating flow (Pulsing and Foaming Flow) or drip (Specified-within-the-article liquid stream, Gas-continuous or Tricking Flow), is preferably drip.Pulsating flow refers to that part and little part that liquid hold-up is large replace mobile state; Drip be liquid because gravity flows down from granules of catalyst with membranaceous, and gas is the state that external phase flows through this space.Along with the flow velocity change of gas-liquid mixed phase stream is large, flow pattern becomes drip from pulsating flow.
In addition, the hop count of reactor fixed bed has multistage, preferably has 3 sections.In deteriorated many situations of solid catalyst, because worsening reason material flows into from inlet portion, cause active site to disappear.As being directed to this countermeasure, can enumerate following manner: each fixed bed is connected in series with 3 individual slots, if occur deterioratedly, thereby replace to connect cyclically, uses.By being set to multistage, the addition of chloroform also can rotation be used, chloroform amount that can inhibition system internal recycle.
As temperature of reaction, if temperature is too low, viscosity uprises, the pressure-losses increases.On the contrary, in the situation of high temperature, chlorine is dissolved into as speed limit, reacts suppressed.Therefore, as temperature of reaction, be 40～130 ℃, more preferably 55～90 ℃.
As reaction pressure, as using 80 ℃ as shown in Fig. 8 of temperature of reaction example, relevant from the addition of chloroform, the PDCB liquid phase rate of recovery, expectation is that 950～1450Torr is (if temperature of reaction is in the scope of 55～90 ℃ to be same.)。
By Fig. 8, can be made judging.That is, (1), once running pressure uprises, if do not improve the ratio of chloroform/benzene, cannot maintain temperature of reaction; (2) more than the pressure of certain service temperature, chloroform can not evaporate, and in order to maintain this temperature, needs a large amount of chloroforms; (3) on the contrary,, below the pressure of certain service temperature, chloroform all evaporates.Now, PDCB evaporates equally; (4) therefore, the condition that chloroform or PDCB remain at the bottom of the tower of reactor is appropriate, preferably in the recovery of chloroform or PDCB can not produce on the ratio of chloroform/benzene the region of large impact, does not operate; Expectation is the region that the ratio of chloroform/benzene is 16～20, the PDCB rate of recovery is 90～95%.
After reaction, in order to reclaim, to recycle in secondary segment having carried out chloroform and the resultant of reaction of adiabatic evaporation, need to carry out cooling.For by chloroform condensing cooling, can use the 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 as below 53 ℃.But, confirm by experiment, because chloroform has played the effect of solvent to PDCB, if therefore have chloroform, near normal temperature, can there is not separating out of PDCB yet.Being reduced to 40 ℃ is not impossible below.
Directly the trichloromethane (chloroform) of heat-eliminating medium reacts and is converted into tetrachloromethane with chlorine.Therefore, thus expectation tetrachloromethane separation from trichloromethane is removed to outside system tetrachloromethane can be accumulated in trichloromethane circulating system.
Then, operation is constructed in desired operation remark additionally.
In resultant of reaction in reactor, contain by product (hydrocarbon compound) and hydrogenchloride.Because the boiling point of hydrogenchloride is-85 ℃, liquids recovery is very difficult, and therefore the mode with the aqueous solution reclaims.The hydrogen cloride concentration expectation of reclaiming is high as far as possible concentration, and the degree of 35%HCl, can easily reclaim if.
That is, the resultant of reaction in reactor is delivered to hydrogenchloride and remove tower, the tower top of removing tower from hydrogenchloride is separated with the hydrocarbon compound accompanying with it by hydrogenchloride; Hydrogenchloride and a small amount of hydrocarbon compound of accompanying with it are delivered to cooling tower, in this cooling tower, by the condenser through attached carry out cooling water-phase component intersperse among in tower, carry out cooling, thereby at the bottom of cooling tower, be separated into water and hydrocarbon compound, in the mode of this separated water-phase component, obtain the 35%HCl aqueous solution.For separated hydrocarbon compound, utilize the knockout tower of back segment to be separated into water and hydrocarbon compound, hydrocarbon compound is recycled.
Resultant of reaction for being gathered in hydrogenchloride and removing at the bottom of the tower of tower, on one side can remove TCB, m-DCB, o-DCB afterwards, Yi Bian make target p-DCB crystallization, carries out commercialization.
The appropriate location that in addition, the liquid in system can be returned to in-process recycles.
(the 1st embodiment)
Then, embodiments of the present invention are described.
Fig. 1 represents the 1st embodiment of the present invention.
10 is reactor, is 3 sections of formations in embodiment.For the benzene 1 as raw material, from the tower top of the reactor 10 of the 1st section, supply with after utilizing as required the not shown moisture means of removing in advance moisture to be removed.
For chlorine 2, in the reactor 10,10,10 of each section, from its tower top, in mode arranged side by side, supply with.In each reactor 10,10,10, set up condenser 12,12,12.Chloroform (heat-eliminating medium) 3 delivered to mixing tank 14 by storage tank, in the reactor 10 that is supplied to the 1st section by its tower top by pump 16.In addition, the recovery chloroform 3A operation below of utilizing the not shown treatment scheme of detailed content being reclaimed and benzene 1 are together supplied with from the tower top of the reactor 10 of the 1st section.In addition, will similarly utilize the recovery chloroform 3B that operation reclaims of the not shown treatment scheme of detailed content to be supplied in described mixing tank 14 below.
In each reactor 10,10,10, zeolite catalyst 18 (formed body) is housed in the mode with fixed bed, stream falls in utilization makes raw material (benzene), chlorine circulation.At reactor 10 perisporiums, be provided with the cooling chuck 11 of using, utilize the heat-eliminating mediums such as water to carry out cooling.
Utilize pump 20,20, successively resultant of reaction is directed into the reactor 10,10 of secondary segment.In reactor 10, utilize condenser 12,12,12 will evaporate composition condensation, then deliver in the reactor 10,10 and mixing tank 14 of secondary segment.A part for uncooled a small amount of resultant of reaction is delivered to cooling tower 24.
Composition at the bottom of the tower of the reactor 10 of terminal section is delivered to hydrogenchloride to be removed in tower 22, by bottom, heat that from hydrogenchloride, to remove the tower top of tower 22 separated with the hydrocarbon compound accompanying with it by hydrogenchloride, delivered to cooling tower 24, in this cooling tower, utilize pump 28 by the condenser through attached 26 carry out cooling water-phase component intersperse among in tower, carry out cooling, thereby in cooling tower 24, be separated into water and hydrocarbon compound, in the mode of this separated water-phase component, obtain the 35%HCl aqueous solution.Hydrocarbon compound for being gathered in the settling bath 30 of 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 be separated into water and hydrocarbon compound, and hydrocarbon compound is recycled.
Resultant of reaction for being gathered in hydrogenchloride and removing at the bottom of the tower of tower 22, can be used suitable processing means afterwards, Yi Bian remove TCB, m-DCB, o-DCB, Yi Bian make target p-DCB crystallization, carries out commercialization.In addition, symbol 32 is drawdown pump.
(the 2nd embodiment)
Fig. 9 represents the 2nd embodiment of the present invention.
Manufacture in the method for santochlor carrying out chlorination using benzene as prepared using chlorine, compare with the speed of response of benzene and chlorine, as the monochloro-benzene of reaction intermediates and the speed of response of chlorine slow (Figure 12), large thereby needed catalytic amount relatively becomes.Therefore, it is large that the reactor 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 manufacture method of following santochlor specifically: described reactor has multistage; The unreacted chlorine of described raw material, heat-eliminating medium, chlorine and/or back segment is supplied in the reactor of first section; The resultant of reaction of leading portion is supplied in the reactor of secondary segment; The chlorine of heat-eliminating medium and excess quantity is supplied in the later reactor of secondary segment; Formation reaction thing by terminal section obtains crude product santochlor.By the method, can improve the speed of response (Figure 12) of monochloro-benzene and chlorine.
In addition, if the chlorine of excess supply amount, in the situation that as the homogeneous catalyst of prior art, contain the dichlorobenzene of santochlor and the chlorine reaction of excess quantity as target resultant, generates trichloro-benzene; But in the present invention,, by using zeolite catalyst, can suppress the generation of trichloro-benzene.As shown in figure 13, even at Cl
2under condition more than/MCB=1.0, carry out the manufacture of santochlor, the chlorination degree of resultant of reaction also stops near 2.0, has suppressed trichloro-benzene building-up reactions.
The reactor 10 of Fig. 9 is 3 sections of formations.For the benzene 1 as raw material, from the tower top of the reactor 10 of the 1st section, supply with after utilizing as required the not shown moisture means of removing in advance moisture to be removed.
Utilize pump 20,20, successively resultant of reaction is directed into the reactor 10,10 of secondary segment.In reactor 10, utilize condenser 12,12,12 will evaporate composition (being mainly heat-eliminating medium) condensation, then deliver to reactor 10,10 and the mixing tank 14 of secondary segment.For the unreacted chlorine in reactor 10 and/or the hydrogenchloride that generated by reaction, from the tower top of the reactor 10 of leading portion, supply with.A part for uncooled a small amount of resultant of reaction and chloroform are supplied in cooling tower 24.
For composition at the bottom of the tower of the reactor 10 of terminal section and deliver to uncooled resultant of reaction and the chloroform of cooling tower 24, flow process is thereafter identical with the 1st embodiment.
(the 3rd embodiment)
Figure 10 represents the 3rd embodiment of the present invention.
The 3rd embodiment has carried out novel motion for the method to each section of base feed.Be following santochlor manufacture method specifically: described reactor has multistage; Described raw material, chlorine and/or heat-eliminating medium are supplied in the reactor of first section; The resultant of reaction of leading portion is separated into unreacting material and resultant, unreacting material is returned in the reactor of leading portion, resultant is supplied in the reactor of secondary segment; Chlorine and heat-eliminating medium are supplied in the later reactor of secondary segment; Resultant of reaction by terminal section obtains santochlor.
Compare with the method that the resultant of reaction of first section does not carry out in the separated reactor that is just supplied to secondary segment, by the method, can improve the para-selectivity (Figure 14) in resultant of reaction.
The reactor 10 of Figure 10 is 2 sections of formations.For the benzene 1 as raw material, from the tower top of the reactor 10 of the 1st section, supply with after utilizing as required the not shown moisture means of removing in advance moisture to be removed.
For chlorine 2, in the reactor 10,10 of each section, in mode arranged side by side, from its tower top, supply with.In each reactor 10,10, set up condenser 12,12.Chloroform (heat-eliminating medium) 3 delivered to mixing tank 14 by storage tank, in the reactor 10 that is supplied to the 1st section by its tower top by pump 16.In addition, the recovery chloroform 3A operation below of utilizing the not shown treatment scheme of detailed content being reclaimed and benzene 1 are together supplied with from the tower top of the reactor 10 of the 1st section.In addition, will similarly utilize the recovery chloroform 3B that operation reclaims of the not shown treatment scheme of detailed content to be supplied in described mixing tank 14 below.
Utilize pump 20,20, successively resultant of reaction is directed into unreacting substance knockout tower 13,13.In reactor 10, utilize condenser 12,12 will evaporate composition (being mainly heat-eliminating medium) condensation, then deliver in the reactor 10 and mixing tank 14 of secondary segment.A part for uncooled a small amount of resultant of reaction and chloroform are delivered to cooling tower 24.
In unreacting substance knockout tower 13, by bottom, heat the unreacting substance of leading portion and the hydrogenchloride accompanying with it are undertaken separated by the tower portion of unreacting substance knockout tower 13.Further utilize condenser 15 to make the evaporation composition condensation in unreacting substance knockout tower 13, then unreacting substance is returned in the reactor 10 of leading portion.A part for uncooled hydrogenchloride and a small amount of unreacting substance is delivered to cooling tower 24.
In cooling tower 24, utilize pump 28 that the condenser through attached 26 is carried out to cooling water-phase component and intersperse among and in tower, carry out coolingly, in cooling tower 24, be separated into thus water and chloroform phase, and obtain the 35%HCl aqueous solution in the mode of this separated water-phase component.For the chloroform phase being gathered in the settling bath 30 of the bottom at the bottom of the tower of being located at cooling tower 24, the knockout tower (not shown) by back segment is separated into water and chloroform, and chloroform is recycled.
Heat-eliminating medium for carrying out the terminal section of autoreactor 10, can utilize condenser 12 to carry out it cooling, is then directed into mixing tank 14, uses it for the supply of new chloroform and uses.
For the resultant of reaction being gathered at the bottom of the tower of unreacting substance knockout tower 13 of terminal section, while can use afterwards suitable processing means to remove TCB, m-DCB, o-DCB makes target p-DCB crystallization carry out commercialization.
(the 4th embodiment)
Figure 11 represents the 4th embodiment of the present invention.
Utilize pump 20,20,20 successively resultant of reaction to be directed into separator 19,19,19.Resultant of reaction and aluminium oxide catalyst are carried out separatedly in separator 19,19,19, the aluminium oxide catalyst after separation is returned in the reactor 10,10,10 of leading portion.To the reactor 10,10 of secondary segment, remove tower 22 supplies with hydrogenchloride and carried out the separated resultant of reaction of aluminium oxide catalyst.Reactor 10,10 or cooling tower 24 to secondary segment are carried interior the produced hydrogen chloride gas of each reactor 10,10,10.
At hydrogenchloride, remove in tower 22, by bottom, heat the tower top that hydrogenchloride is removed to tower 22 with the hydrocarbon compound accompanying with it from hydrogenchloride separated, delivered in cooling tower 24, in this cooling tower 24, utilize pump 28 by the condenser through attached 26 carry out cooling water-phase component intersperse among in tower, carry out cooling, in cooling tower 24, be separated into thus water and hydrocarbon compound, in the mode of this separated water-phase component, obtain the 35%HCl aqueous solution.For the hydrocarbon compound that is gathered in the settling bath 30 of the bottom at the bottom of the tower of being located at cooling tower 24, the knockout tower (not shown) by back segment is separated into water and hydrocarbon compound, and hydrocarbon compound is recycled.
For the resultant of reaction that is gathered in hydrogenchloride and removes at the bottom of the tower of tower 22, while can use afterwards suitable processing means to remove TCB, m-DCB, o-DCB makes target p-DCB crystallization carry out commercialization.
Embodiment
(embodiment 1)
According to the flow process of Fig. 1, using benzene as raw material, utilize chlorine to carry out chlorination, manufacture santochlor.In reactor, the aluminum oxide formed body of BEA zeolite is housed in the mode with fixed bed.
In temperature of reaction, be that 75 ℃, pressure are 1.8kg/cm
2condition under carry out chlorination reaction.As chlorination degree, be about 2.0.
The selectivity of the p-DCB obtaining is 77.7%, with highly selective, has stably manufactured p-DCB.
(embodiment 2)
According to the flow process of Fig. 9, using benzene as raw material, utilize chlorine to carry out chlorination, manufacture santochlor.In reactor, the silicon-dioxide formed body of BEA zeolite catalyst is housed in the mode with fixed bed.
In temperature of reaction, be that 80 ℃, pressure are 1.8kg/cm
2condition under carry out chlorination reaction.As chlorination degree, be about 2.0.
The selectivity of the p-DCB obtaining is 74.6%, with highly selective, has stably manufactured p-DCB.
(embodiment 3)
According to the flow process of Figure 10, using benzene as raw material, utilize chlorine to carry out chlorination, manufacture santochlor.In reactor, the silicon-dioxide formed body of BEA zeolite catalyst is housed in the mode with fixed bed.
In temperature of reaction, be that 80 ℃, pressure are 1.8kg/cm
2condition under, carry out chlorination reaction.As chlorination degree, be about 2.0.
The selectivity of the p-DCB obtaining is 74.6%, with highly selective, has stably manufactured p-DCB.
(embodiment 4)
According to the flow process of Figure 11, using benzene as raw material, utilize chlorine to carry out chlorination, manufacture santochlor.In reactor, take to starch the silicon-dioxide formed body that the granulation of BEA zeolite catalyst is 0.8～3.2mm is housed in the mode of state bed.
In temperature of reaction, be that 80 ℃, pressure are 1.8kg/cm
2condition under carry out chlorination reaction.As chlorination degree, be about 2.0.
The selectivity of the p-DCB obtaining is 72.5%, with highly selective, has stably manufactured p-DCB.
(comparative example)
Illustrate as the existing methodical homogeneous catalyst iron(ic) chloride FeCl that used
3comparative example.As 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 are also supplied to wherein, while utilize water coolant unit 53 to carry out cooling reaction through chuck 51.The resultant of reaction that comes from bottom stockpiles in reservoir 54 after cooling; The gas-liquid composition that comes from top stockpiles in reservoir 55 after cooling.
Reaction conditions is as 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 resultant that is represented the chlorination of the benzene in this reaction process by reaction degree of carrying out (chlorination degree) changes, and obtains thus Figure 16.
As shown in Figure 16, the reaction of homogeneous catalyst is progressively to carry out with parallel mode.As its reason, it is believed that it is due to homogeneous catalyst, there is no the resistance of diffusion, so benzene and monomer or monomer and disome react simultaneously.Therefore, the disome selectivity maximum in reaction rests on 80%.
The optionally variation that is accompanied by the PDCB in DCB productive rate DCB is shown in to Figure 17; The passing that is accompanied by chlorination PDCB productive rate is shown in to Figure 18.Because homogeneous catalyst does not have sterically hinderedly in ortho position-para-orientation, therefore as shown in figure 17, contraposition body selectivity is 60%, is lower value.In addition, as shown in figure 18, because disome selectivity maximum rests on 80%, therefore the contraposition body maximum yield in reaction is 50%.
Temperature is dropped to 70 ℃ from 80 ℃ of the temperature of reaction of standard conditions tests.Show the result in Figure 19.Even known reduction temperature of reaction, contraposition body selectivity does not change yet.
Then, catalytic amount is reduced to approximately 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 known activity of result does not change; As shown in figure 20, can be organized into a curve, selectivity does not change yet.
As mentioned above, known as long as use homogeneous catalyst, just cannot manufacture p-DCB with highly selective.
Industrial utilization
According to the present invention, can obtain continuously as the extremely high compound of the industrial value of PPS raw material.
Nomenclature
1 ... benzene, 2 ... chlorine, 10 ... reactor, 11 ... chuck, 12 ... condenser, 18 ... zeolite catalyst, 20 ... pump, 22 ... hydrogenchloride is removed tower, 24 ... cooling tower, 26 ... condenser, 28 ... pump, 30 ... settling bath, 32 ... drawdown pump.
Claims (10)
1. the manufacture method of a santochlor, it is to using at least one of benzene and monochloro-benzene to carry out as raw material and with chlorine the method that santochlor is manufactured in chlorination, this manufacture method is characterised in that, above-mentioned raw materials and above-mentioned chlorine are directed in the reactor being equipped with in the mode with fixed bed containing the catalyzer of zeolite, utilization be take moulding base that alumina sol is principal constituent zeolite is carried out to catalyzer that moulding obtains as above-mentioned catalyzer
Wherein, at least one heat-eliminating medium of methyl chloride and monochloroethane is directed into each section of described reactor, makes above-mentioned heat-eliminating medium evaporation, the temperature that suppresses described chlorination reaction rises.
2. the manufacture method of a santochlor, it is to using at least one of benzene and monochloro-benzene to carry out as raw material and with chlorine the method that santochlor is manufactured in chlorination, this manufacture method is characterised in that, in the interior reactor with multistage being equipped with containing the catalyzer of zeolite, the unreacted chlorine of above-mentioned raw materials, chlorine and/or back segment is supplied in the reactor of first section; The resultant of reaction of leading portion is supplied in the reactor of secondary segment; The chlorine of excess quantity is supplied in the later reactor of secondary segment; Formation reaction thing by terminal section obtains santochlor,
Wherein, at least one heat-eliminating medium of methyl chloride and monochloroethane is directed into each section of described reactor, makes above-mentioned heat-eliminating medium evaporation, the temperature that suppresses described chlorination reaction rises.
3. the manufacture method of a santochlor, it is to using at least one of benzene and monochloro-benzene to carry out as raw material and with chlorine the method that santochlor is manufactured in chlorination, this manufacture method is characterised in that, in the interior reactor with multistage being equipped with containing the catalyzer of zeolite, above-mentioned raw materials, chlorine are supplied in the reactor of first section; The resultant of reaction of leading portion is separated into unreacting material and resultant, unreacting material is returned in the reactor of leading portion, resultant is supplied in the reactor of secondary segment; Chlorine is supplied in the later reactor of secondary segment; Resultant of reaction by terminal section obtains santochlor,
Wherein, at least one heat-eliminating medium of methyl chloride and monochloroethane is directed into each section of described reactor, makes above-mentioned heat-eliminating medium evaporation, the temperature that suppresses described chlorination reaction rises.
4. the manufacture method of santochlor claimed in claim 1, wherein, described zeolite is proton type zeolite.
5. the manufacture method of santochlor claimed in claim 1, wherein, described zeolite is zeolite beta.
6. the manufacture method of santochlor claimed in claim 1, wherein, described zeolite is MFI type zeolite.
7. the manufacture method of the santochlor described in claim 1～3 any one, wherein, the vaporised gas composition of described heat-eliminating medium, in reactor condensed exterior, recycles this phlegma as described heat-eliminating medium.
8. the manufacture method of santochlor claimed in claim 1, wherein, utilizes and falls stream and makes described raw material and chlorine circulation.
9. the manufacture method of santochlor claimed in claim 1, wherein, described chlorination reaction is that 40～130 ℃, pressure are to carry out below 10atm in temperature.
10. the manufacture method of santochlor claimed in claim 1, wherein, described reactor has multistage; Chlorine is supplied in each reactor in mode arranged side by side; Described raw material and chlorine are supplied in the reactor of first section; The resultant of reaction of leading portion is supplied in the reactor of secondary segment; Chlorine is supplied in the later reactor of secondary segment in mode arranged side by side; Resultant of reaction by terminal section obtains santochlor.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-077002 | 2009-03-26 | ||
| JP2009-077004 | 2009-03-26 | ||
| JP2009-077003 | 2009-03-26 | ||
| JP2009077003A JP5366610B2 (en) | 2009-03-26 | 2009-03-26 | Method for producing paradichlorobenzene |
| JP2009-077001 | 2009-03-26 | ||
| JP2009077001A JP5425503B2 (en) | 2009-03-26 | 2009-03-26 | Method for producing paradichlorobenzene |
| JP2009077002A JP5474389B2 (en) | 2009-03-26 | 2009-03-26 | Method for producing paradichlorobenzene |
| JP2009077004A JP5669362B2 (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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102361841A CN102361841A (en) | 2012-02-22 |
| CN102361841B true CN102361841B (en) | 2014-04-09 |
Family
ID=42780856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080013416.7A Active CN102361841B (en) | 2009-03-26 | 2010-03-18 | Process for production of p-dichlorobenzene |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN102361841B (en) |
| TW (1) | TWI535683B (en) |
| WO (1) | WO2010110163A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4365158A1 (en) | 2022-11-04 | 2024-05-08 | PCC ROKITA Spolka Akcyjna | Method of selective paradichlorobenzene preparation with improved catalytic system recovery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0653689B2 (en) * | 1986-01-31 | 1994-07-20 | 東ソー株式会社 | Process for producing para-substituted halogenated benzene derivative |
| JPH0817944B2 (en) * | 1986-12-29 | 1996-02-28 | 東ソー株式会社 | Zeolite catalyst compact for liquid phase organic reaction |
| JPH0317036A (en) * | 1989-06-14 | 1991-01-25 | Color Chem Kogyo Kk | Continuous reactor for halogenated benzenes and continuous production system and process using the same |
| JPH04253929A (en) * | 1991-02-05 | 1992-09-09 | Kureha Chem Ind Co Ltd | Production of para-dichlorobenzene |
| JP4162732B2 (en) * | 1997-02-05 | 2008-10-08 | 千代田化工建設株式会社 | Method for producing p-dichlorobenzene |
| JP2001213815A (en) * | 2000-02-03 | 2001-08-07 | Tosoh Corp | Method for producing para-dichlorobenzene |
| JP2004107318A (en) * | 2002-05-27 | 2004-04-08 | Toray Ind Inc | Method for halogenating benzene and benzene derivative |
-
2010
- 2010-03-18 CN CN201080013416.7A patent/CN102361841B/en active Active
- 2010-03-18 WO PCT/JP2010/054647 patent/WO2010110163A1/en active Application Filing
- 2010-03-22 TW TW099108312A patent/TWI535683B/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|---|
| TWI535683B (en) | 2016-06-01 |
| TW201035007A (en) | 2010-10-01 |
| CN102361841A (en) | 2012-02-22 |
| WO2010110163A1 (en) | 2010-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102216245B (en) | Process for the manufacture of hydrofluoroolefins | |
| CN103209942A (en) | Process for producing trans-1,3,3,3-tetrafluoropropene | |
| CN103172488B (en) | Prepare the method for fluorinated organic compounds | |
| CN101500973A (en) | Halocarbon production processes, halocarbon separation processes, and halocarbon production systems | |
| CN101821220B (en) | Method for producing trans-1,3,3,3-tetrafluoropropene | |
| CN103724155B (en) | A kind of production technique of propenyl chloride | |
| CN101351426B (en) | Method for producing fluorinated organic compounds | |
| JP6364029B2 (en) | Method for producing 1,1,2,3-tetrachloropropene | |
| CN102099316A (en) | Continuous process for converting natural gas to liquid hydrocarbons | |
| CN107793290A (en) | The manufacture method of fluorine-containing alkane | |
| CN100546959C (en) | 1,1,1,3, the production method of 3-pentafluoropropane | |
| CN102361841B (en) | Process for production of p-dichlorobenzene | |
| CN1270575A (en) | Method for producing perhalogenated cyclopentene | |
| CN107635916A (en) | For preparing double (fluorosulfonyl) imido methods | |
| JP5159245B2 (en) | Method for producing paradichlorobenzene | |
| CN102405201B (en) | Process for producing paradichlorobenzene | |
| CN104411667B (en) | The manufacture method of 1,3,3,3-tetrafluoropropene | |
| CN104703954A (en) | Method for producing difluoromethane | |
| CN105939986B (en) | Method for manufacturing hydro-chloro fluoroolefin | |
| JP5366610B2 (en) | Method for producing paradichlorobenzene | |
| CN112939812B (en) | Chlorothalonil production process | |
| JP5669362B2 (en) | Method for producing paradichlorobenzene | |
| JP5474389B2 (en) | Method for producing paradichlorobenzene | |
| JP5425503B2 (en) | Method for producing paradichlorobenzene | |
| JP4100893B2 (en) | Continuous production method of cyclododecanone compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |