CN108640814A - A kind of method of glycerin chlorination synthesizing dichloropropanol - Google Patents

A kind of method of glycerin chlorination synthesizing dichloropropanol Download PDF

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Publication number
CN108640814A
CN108640814A CN201810349526.9A CN201810349526A CN108640814A CN 108640814 A CN108640814 A CN 108640814A CN 201810349526 A CN201810349526 A CN 201810349526A CN 108640814 A CN108640814 A CN 108640814A
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catalyst
weight
hzsm
content
carrier
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王飞利
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Foshan Flying Information Technology Co Ltd
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Foshan Flying Information Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • 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
    • B01J29/42—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 containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of catalyst for glycerin chlorination synthesizing dichloropropanol, using the Cu-Sn/HZSM-5 catalyst of support type, it is carried on the surface of carrier HZSM-5 using base metal Cu and Sn as active component, in dichlorohydrin production process, catalyst is only added when driving and starting, and additive amount is the 0.5~7%wt, preferably 1~2%wt of glycerin weight, circulating and recovering when normal operation, is no longer added.The advantages that new catalyst reaction rate of the present invention is fast, hydrogen chloride utilization rate is high, product yield is high, catalyst amount is few and suitable large-scale industrial production.

Description

A kind of method of glycerin chlorination synthesizing dichloropropanol
Technical field
The present invention relates to field of compound preparation, and in particular to a kind of support type for glycerin chlorination synthesizing dichloropropanol Cu-Sn/HZSM-5 catalyst.
Background technology
Dichlorohydrin is also known as glycerin dichlorohydrin, is that synthesis antiviral drugs " Ganciclovir " is (viral for treating organs transplanting Infection, AIDS etc.), the 1,3- dichloroacetones raw material of high-efficiency low-toxicity deep antifungal Fluconazole (famotidine), crosslinking The raw material of a variety of chemical products such as agent, water treatment agent.Dichlorohydrin is the intermediate for producing epoxychloropropane, has also been important Machine raw material.In recent years, to the rapid growth of epoxy resin demand, the development of epoxychloropropane, epoxy chloropropionate are effectively promoted The development of alkane has driven the development of dichlorohydrin production technology and the expansion in market again.
The method of industrialized production epoxychloropropane mainly has chlorohydrination, allyl acetate method at present.There are about 50 for chlorohydrination Year history, accounts for the 95% of epoxychloropropane (ECH) total output；The shortcomings that chlorohydrination is that chlorine consumption is high, material consumption is high, energy consumption is big；If Standby seriously corroded, maintenance cost are high；Product by-product is more, generates a large amount of organic chloride waste water and (often produces 1tECH and about generate 50 ~60m3 waste water).Acetate propylene ester process is the technique of exploitation the 1980s, accounts for about the 5% of ECH total outputs.Acetate propylene The shortcomings that ester process is that technological process is longer, and catalyst service life is short, equipment corrosion, needs the anti-acetic acid corrosion of stainless steel material, Prevent allyl alcohol unit gaseous mixture from exploding, one-time investment expense is relatively high.
In addition, since crude oil price is high, various countries greatly develop biodiesel industry, and a large amount of biologies of by-product are sweet therewith Oily (account for biodiesel amount 1/10) causes glycerol market surplus, price to slump；And the global epoxychloropropane of another aspect is very In short supply, preparing dichloropropanol by glycerol method obtains new machine in this background.Epoxychloropropane or dichlorohydrin are produced using glycerine method, Depending on using petroleum resources as raw material has been broken away from, and has saved a large amount of petroleum resources, has also reduced environmental pollution.Relative to stone Oil process produces for dichlorohydrin, and equipment investment greatly reduces, and for this Chinese each and every one large agricultural country, makes full use of farming Object living resources, convenient for recycling and economic sustainable development for resource.
In the existing method for preparing dichlorohydrin, mainly using organic acid as catalyst, and be aided with organic nitrile, acid anhydrides etc. into Row chlorination reaction, but due to the characteristics of organic acid is not easily recycled, is not readily separated but also catalyst consumption is larger, and glycerine Conversion ratio be also greatly affected.In order to overcome above-mentioned difficulties, suitable catalyst is carried out at present many Research, as Chinese patent CN104151139A discloses the side that a kind of HY types molecular sieve catalytic glycerin chlorination prepares dichlorohydrin Method；Chinese patent CN104163753A discloses a kind of method that modified L-type molecular sieve catalytic glycerin chlorination prepares dichlorohydrin, So that the total recovery of dichlorohydrin is further promoted.
In addition to this, due to being reversible reaction, for break reaction balance, make reaction to be conducive to generate product direction into Row, must just remove product.Therefore, a variety of glycerine continuous chlorinations that are suitable for have been developed in the prior art generates two chloroethenes The device of alcohol, as disclosed a kind of continuous method for preparing dichlorohydrin in Chinese patent CN101979365A, this method is equal Under phase catalyst effect, the hydrogen chloride of glycerine carries out in reactive distillation column, reacts and detaches and is all carried out in conversion zone, adopts With conventional rectification under vacuum method from reaction product separating dichloropropanol and catalyst, while so that reaction product water is generated just It is removed by part dichlorohydrin azeotropic separation, to constantly break balance, increases the motive force of reaction, reaction is made to be produced to generation The direction of object dichlorohydrin is developed, and so that the reaction of raw materials glycerine almost all is generated dichlorohydrin, substantially increases dichloro third The yield of alcohol；And the HCl in tail gas can then be recycled in tower that the reaction was continued, substantially increase the utilization rate of HCl.As it can be seen that reaction The improvement of device also has having certain effect for the production of dichlorohydrin.But also can for depending on unduly for particular reactor The development restriction for causing dichlorohydrin industry influences the extensive industrialization of medium-sized and small enterprises；Meanwhile the yield of dichlorohydrin product Also still expect further improve.
Invention content
For this purpose, technical problem to be solved by the present invention lies in a kind of method that glycerin chlorination produces dichlorohydrin is provided, To solve the problems, such as that dichlorohydrin prepares poor selectivity in reaction, catalyst recycling difficulty in the prior art.
In order to solve the above technical problems, the present invention provides a kind of support type for glycerin chlorination synthesizing dichloropropanol Cu-Sn/HZSM-5 catalyst, by base metal Cu and Sn as active component, HZSM-5 is formed as carrier for it, Cu and Sn's Weight ratio is 1：0.1‐10；Preferably, the weight ratio of Cu and Sn is 1：0.3-8, with urging for the glycerin chlorination refining dichlorohydrin On the basis of the total weight of agent, the content of Cu is 5-25 weight % for the content of 1-25 weight %, Sn and the content of carrier is 50-94 weight %；Preferably, the content of Cu is that the content of 7-23 weight %, Sn are 5-20 weight % and the content of carrier is 57-88 weight %.
The Cu-Sn/HZSM-5 catalyst of the support type uses base metal Cu and Sn as active component, can be effective Ground improves glycerol conversion yield, dichlorohydrin selectivity and the yield in glycerin chlorination reaction.Under preferable case, the weight of Cu and Sn Than being 1：0.1‐10；Preferably, the weight ratio of Cu and Sn is 1：0.3‐8.Particularly, the content of Cu and Sn exists in the catalyst When in above range, the improvement that catalyst reacts glycerin chlorination is more preferable.
The present invention also provides a kind of methods for the catalyst preparing glycerin chlorination refining dichlorohydrin provided by the invention, should Method includes：(1) compound containing Cu and compound containing Sn are introduced in carrier HZSM-5, obtain catalyst precarsor；It (2) will be described Catalyst precarsor restores under hydrogen atmosphere, obtains the catalyst of glycerin chlorination refining dichlorohydrin.
What is provided in method provided by the invention introduces compound containing Cu and compound containing Sn, purpose in carrier HZSM-5 It is finally to introduce active component, specially Cu and Sn into the catalyst of the glycerin chlorination refining dichlorohydrin of preparation.
In the case of, according to the invention it is preferred to, the addition of the compound containing Cu, compound containing Sn and carrier HZSM-5 makes In the catalyst of the obtained glycerin chlorination refining dichlorohydrin, with the gross weight of the catalyst of the glycerin chlorination refining dichlorohydrin On the basis of amount, the content of Cu is 5-25 weight % for the content of 1-25 weight %, SN and the content of carrier is 50-94 weights Measure %；Preferably, the content of Cu is that the content of 7-23 weight %, Sn are 5-20 weight % and the content of carrier is 57-88 weights Measure %.
According to the present invention, the compound containing Cu can be that carrier HZSM-5 can be added to obtain catalyst precarsor and in step Suddenly it can be changed into the substance of Cu under conditions of the reduction in (2)；Under preferable case, the compound containing Cu is ferric nitrate, chlorine Change at least one of iron, frerrous chloride, ferrous nitrate.
According to the present invention, the compound containing Sn can be that carrier can be added to obtain catalyst precarsor and in step (2) In reduction under conditions of can be changed into the substance of Sn.Under preferable case, the compound containing Sn is butter of tin or chlorination Stannous.
The regeneration method of the Cu-Sn/HZSM-5 catalyst of the support type is off into ethyl acetate raw material, continues to lead to Enter hydrogen, is 100~1000h in 300 DEG C~600 DEG C of temperature, 0.8~6.0MPa of pressure, hydrogen volume air speed‐1Under the conditions of to lose Catalyst living carries out in reactor plus hydrogen regeneration 3~for 24 hours.
The present invention is as follows using the concrete technology of above-mentioned catalyst glycerin chlorination：By the Cu-Sn/ of glycerine and support type HZSM-5 catalyst is added in chlorination reaction system carries out chlorination reaction with hydrogen chloride, and chlorination reaction system can be more kettles Series connection or multitower series connection continuous production processes, or intermittent caldron process or tower technique.Chlorination reaction terminates Afterwards, chlorated liquid steams dichlorohydrin, heavy constituent (predominantly catalyst, a glycerin chlorohydrin, glycerine) circulating and recovering by distillation.It is described Operation temperature is 60~130 DEG C, and preferably 100~110 DEG C, operating pressure is 20~100kPa, preferably 40~60kPa.It opens for the first time The 0.5~7% of qualities of glycerin, preferably 1~2% are disposably added when vehicle, normal operating state circulating and recovering no longer adds.
Further, the reaction is carried out in the reactor of two or more serial or parallel connections, each reactor The identical or different catalyst of interior filling.
A kind of advantageous effect of the method for glycerin chlorination synthesizing dichloropropanol of the present invention is mainly reflected in：Support type Cu-Sn/HZSM-5 catalyst price compared with low activity height, glycerin chlorination synthesizing dichloropropanol high catalytic efficiency, hydrogen chloride utilize Rate is high, high selectivity, and product yield is high；Catalyst is disposably put into when need to only drive, so that it may be recycled, be reduced catalyst Dosage and recycling etc. expenses, do not generate harmful waste water or waste residue, it is environmentally protective.
Specific implementation mode
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects It encloses.
【Embodiment 1】
A certain amount of ferric nitrate and butter of tin and deionized water are mixed evenly, it is molten to obtain the dipping containing Cu-Sn Liquid；A certain amount of α-HZSM-5 carriers are added in above-mentioned dipping solution, stand aging for 24 hours at room temperature, then through 80 DEG C of dry 4h, 700 DEG C of roasting 4h, are made catalyst precarsor；
Catalyst precarsor is restored, reduction temperature is 400 DEG C, recovery time 10h, and hydrogen contains in hydrogen atmosphere Amount is 15 volume %, and the volume space velocity of hydrogen atmosphere is 2000h‐1, obtain catalyst I.By adjusting active component and carrier Dosage so that the group of catalyst I becomes：The content of content 5.6 the weight %, HZSM-5 of content 10.5 the weight %, Sn of Cu 83.9 weight %.
【Embodiment 2】
A certain amount of ferric nitrate and butter of tin and deionized water are mixed evenly, it is molten to obtain the dipping containing Cu-Sn Liquid；A certain amount of HZSM-5 carriers are added in above-mentioned dipping solution, stand aging for 24 hours at room temperature, then through 80 DEG C of dry 4h, 700 DEG C of roasting 4h, are made catalyst precarsor；
Catalyst precarsor is restored, reduction temperature is 400 DEG C, recovery time 10h, and hydrogen contains in hydrogen atmosphere Amount is 15 volume %, and the volume space velocity of hydrogen atmosphere is 2000h‐1, obtain catalyst II.By adjusting active component and carrier Dosage so that the group of catalyst II becomes：The content of content 12.1 the weight %, HZSM-5 of content 6.6 the weight %, Sn of Cu 81.1 weight %.
【Embodiment 3】
A certain amount of ferric nitrate and butter of tin and deionized water are mixed evenly, it is molten to obtain the dipping containing Cu-Sn Liquid；A certain amount of HZSM-5 carriers are added in above-mentioned dipping solution, stand aging for 24 hours at room temperature, then through 80 DEG C of dry 4h, 700 DEG C of roasting 4h, are made catalyst precarsor；
Catalyst precarsor is restored, reduction temperature is 400 DEG C, recovery time 10h, and hydrogen contains in hydrogen atmosphere Amount is 15 volume %, and the volume space velocity of hydrogen atmosphere is 2000h‐1, obtain catalyst III.By adjusting active component and load The dosage of body so that the group of catalyst III becomes：The 12.1 weight % of content of content 8.6 the weight %, Sn of Cu, HZSM-5's 79.3 weight % of content.
【Embodiment 4】
A certain amount of ferric nitrate and butter of tin and deionized water are mixed evenly, it is molten to obtain the dipping containing Cu-Sn Liquid；A certain amount of α-HZSM-5 carriers are added in above-mentioned dipping solution, stand aging for 24 hours at room temperature, then through 80 DEG C of dry 4h, 700 DEG C of roasting 4h, are made catalyst precarsor；
Catalyst precarsor is restored, reduction temperature is 400 DEG C, recovery time 10h, and hydrogen contains in hydrogen atmosphere Amount is 15 volume %, and the volume space velocity of hydrogen atmosphere is 2000h-1, obtains catalyst IV.By adjusting active component and load The dosage of body so that the group of catalyst I becomes：Content 8.5 the weight %'s, HZSM-5 of content 12.5 the weight %, Sn of Cu contains Measure 79 weight %.
【Embodiment 3】
The Cu-Sn/HZSM-5 catalyst of glycerine and support type is added in chlorination reaction system and is carried out with hydrogen chloride Chlorination reaction, it is 100 DEG C that chlorination reaction system, which uses caldron process, operation temperature, operating pressure 60kPa；When driving for the first time 2% catalyst of disposable addition qualities of glycerin, after chlorination reaction, chlorated liquid steams dichlorohydrin by distillation, weighs Component circulating and recovering.The catalytic performance of catalyst is evaluated, experimental result is listed in table 1.
Table 1
Above description has fully disclosed the specific implementation mode of the present invention.It should be pointed out that being familiar with the field Technical staff is to any change for being done of specific implementation mode of the present invention all without departing from the range of claims of the present invention. Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.

Claims (5)

1. a kind of catalyst of glycerin chlorination refining dichlorohydrin, it is characterised in that：It is by base metal Cu and Sn as activearm Point, the Cu-Sn/HZSM-5 catalyst for the support type that HZSM-5 is formed as carrier,
Wherein, the weight ratio of Cu and Sn is 1：0.1‐10；Preferably, the weight ratio of Cu and Sn is 1：0.3-8, with the glycerine chlorine On the basis of the total weight for changing the catalyst of refining dichlorohydrin, the content of Cu is that the content of 1-25 weight %, Sn are 5-25 weight %, And the content of carrier is 50-94 weight %；Preferably, it is 5-20 weight % that the content of Cu, which is the content of 7-23 weight %, Sn, And the content of carrier is 57-88 weight %.
2. the catalyst of glycerin chlorination refining dichlorohydrin according to claim 1, which is characterized in that the support type The preparation method of Cu-Sn/HZSM-5 catalyst is：(1) compound containing Cu and compound containing Sn are introduced in carrier HZSM-5, are obtained To catalyst precarsor；(2) catalyst precarsor is restored under hydrogen atmosphere, obtains urging for glycerin chlorination refining dichlorohydrin Agent.
3. the catalyst of glycerin chlorination refining dichlorohydrin according to claim 1, which is characterized in that the compound containing Cu Can be that carrier HZSM-5 can be added to obtain that under conditions of catalyst precarsor and reduction in step (2) Cu can be changed into Substance；Under preferable case, the compound containing Cu is at least one in ferric nitrate, iron chloride, frerrous chloride, ferrous nitrate Kind.
4. the catalyst of glycerin chlorination refining dichlorohydrin according to claim 1, it is characterised in that：The compound containing Sn It can be the object that carrier can be added and obtain that Sn can be changed under conditions of catalyst precarsor and reduction in step (2) Matter；Under preferable case, the compound containing Sn is butter of tin or stannous chloride.
5. the catalyst of glycerin chlorination refining dichlorohydrin according to claim 1, it is characterised in that：The Cu-Sn/ The regeneration method of HZSM-5 catalyst is off into ethyl acetate raw material, continues to be passed through hydrogen, in 300 DEG C~600 DEG C of temperature, pressure 0.8~6.0MPa of power, hydrogen volume air speed are 100~1000h‐1Under the conditions of to decaying catalyst carry out reactor in plus hydrogen regeneration 3~for 24 hours.
CN201810349526.9A 2018-04-18 2018-04-18 A kind of method of glycerin chlorination synthesizing dichloropropanol Pending CN108640814A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101805243A (en) * 2010-05-07 2010-08-18 宁波东港电化有限责任公司 Production method of dichloropropanol
CN103333047A (en) * 2013-07-09 2013-10-02 南京奥凯化工科技有限公司 Preparation method of dichloropropanol
CN103464178A (en) * 2013-07-09 2013-12-25 南京奥凯化工科技有限公司 AG-01 catalyst used for synthesis of dichloropropanol by hydrochlorination of glycerin
CN108440247A (en) * 2018-03-27 2018-08-24 佛山市飞程信息技术有限公司 A kind of method of glycerin chlorination synthesizing dichloropropanol

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101805243A (en) * 2010-05-07 2010-08-18 宁波东港电化有限责任公司 Production method of dichloropropanol
CN103333047A (en) * 2013-07-09 2013-10-02 南京奥凯化工科技有限公司 Preparation method of dichloropropanol
CN103464178A (en) * 2013-07-09 2013-12-25 南京奥凯化工科技有限公司 AG-01 catalyst used for synthesis of dichloropropanol by hydrochlorination of glycerin
CN108440247A (en) * 2018-03-27 2018-08-24 佛山市飞程信息技术有限公司 A kind of method of glycerin chlorination synthesizing dichloropropanol

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