CN102491877A - Method for producing dichlorhydrin by means of glycerin hydrochlorination - Google Patents
Method for producing dichlorhydrin by means of glycerin hydrochlorination Download PDFInfo
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- CN102491877A CN102491877A CN2011104124137A CN201110412413A CN102491877A CN 102491877 A CN102491877 A CN 102491877A CN 2011104124137 A CN2011104124137 A CN 2011104124137A CN 201110412413 A CN201110412413 A CN 201110412413A CN 102491877 A CN102491877 A CN 102491877A
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- CN
- China
- Prior art keywords
- dichlorohydrine
- gac
- produced
- activated carbon
- glycerol hydrochlorination
- Prior art date
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Links
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 59
- 238000007038 hydrochlorination reaction Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000009471 action Effects 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 150000002978 peroxides Chemical class 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 230000001413 cellular effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 20
- 239000007788 liquid Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 8
- VZIQXGLTRZLBEX-UHFFFAOYSA-N 2-chloro-1-propanol Chemical compound CC(Cl)CO VZIQXGLTRZLBEX-UHFFFAOYSA-N 0.000 description 7
- 238000004438 BET method Methods 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- -1 carboxylate salt Chemical class 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- MLHOXUWWKVQEJB-UHFFFAOYSA-N Propyleneglycol diacetate Chemical compound CC(=O)OC(C)COC(C)=O MLHOXUWWKVQEJB-UHFFFAOYSA-N 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002196 fatty nitriles Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical class CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of chemical engineering, and discloses a catalyst and a method for producing dichlorhydrin by means of glycerin hydrochlorination. The method includes that the dichlorhydrin can be efficiently produced by means of reaction of glycerin and hydrogen chloride under the action of activated carbon or an activated carbon catalyst subjected to modification treatment of hydrogen peroxide, sulfuric acid and the like. The catalyst which is solid is high in activity, easy to be separated from a product and recyclable. The method has the advantages of simplicity in process and low production cost.
Description
Technical field
The invention belongs to chemical field, relate to the Catalyst And Method that a kind of glycerol hydrochlorination is produced dichlorohydrine, relate to a kind of glycerine is produced dichlorohydrine under the activated-carbon catalyst effect method specifically.
Background technology
Dichlorohydrine is claimed glycerin dichlorohydrin again, is the important source material of synthesizing epoxy chloropropane, linking agent, water conditioner and medicine.The working method of dichlorohydrine mainly contains three kinds of propylene high-temperature chlorinations, propylene acetate method, glycerol hydrochlorination method.Propylene high-temperature chlorination and propylene acetate method are to be starting raw material with petroleum cracking product propylene, and along with rising violently of the in short supply and oil price of petroleum resources, production cost is increasingly high.In recent years, because the rise of biofuel industry, the glycerine output of by-product increases suddenly, and the glycerol hydrochlorination method becomes the dichlorohydrine new preparation process route that has competitive power.
Chinese patent CN100999443A discloses the method that glycerine and hydrogen chloride gas prepare dichlorohydrine continuously; The catalyzer of selecting for use is that boiling point is higher than 200 ℃ carboxylic acid, carboxylic acid anhydride, carboxylic acid chloride, carboxylate salt or carboxylicesters, and catalyst levels is usually greater than 1mol/kg (catalyst concentration in every kilogram of liquid).The recovery of this organic catalyst is lower, and catalyzer such as carboxylic acid, carboxylic acid anhydride, carboxylic acid chloride are prone to react with glycerine and cause catalyzer to lose activity.
It is catalyzer that Chinese patent CN101029000A then adopts fatty nitrile or fragrant nitrile; But before in glycerine, feeding hydrogen chloride gas; The catalyzer organic nitrile need activation under temperature of reaction in 30% hydrochloric acid soln, and complex operation, organic nitrile catalyzer contain the CN-of severe toxicity in reacted raffinate; Environmental pollution is serious, the wastewater treatment difficulty.
Chinese patent CN101215223A discloses with the Polyaromatic Ether Sulfone Ether Ketone Ketone resin and the carboxylic acid of band carboxyl side group composite, the method for catalyzing glycerol highly selective synthesizing dichloropropanol, though resin catalyst is reusable, the preparation cost of resin catalyst is higher.
(Catalysis Communications, 2008,9 (9): 1920-1923.) adopt phosphato-molybdic heteropolyacid is catalyzer to Lee etc., under condition of high voltage, prepares dichlorohydrine with aqueous hydrochloric acid and glycerine reaction.This method is owing to exist a large amount of water in the system, and the reaction times needs more than the 20h, also can produce such as by products such as propenal, chloropropanes simultaneously, and the usage quantity of catalyzer is very big, has reached 120% of raw material qualities of glycerin.
Above-mentioned is the method that raw material adopts catalysis synthesizing dichloropropanols such as organic acid, organic nitrile, phospho-molybdic acid with glycerine; All exist catalyzer to be prone to generate multiple by product, cause sepn process complicated, and the catalyst recovery difficulty is big with raw material; Make production cost high, environmental pollution is bigger.
Summary of the invention
The purpose of this invention is to provide a kind of glycerine and under gac class catalyst action, produce the method for dichlorohydrine with hcl reaction.
The objective of the invention is to realize through following technical proposal:
A kind of glycerol hydrochlorination is produced the method for dichlorohydrine, this method be glycerine with hydrogenchloride under gac class catalyst action, under 80～180 ℃, the method for reaction 3～80h production dichlorohydrine.Wherein catalyst levels is 0.5～30% of qualities of glycerin in mass.The flow of hydrogenchloride is 0.5～15mL/ (ming
Glycerine).Reaction is reclaimed catalyzer with reacting liquid filtering after finishing, and filtrating is carried out rectification and purification, can obtain dichlorohydrine.Glycerol hydrochlorination of the present invention is produced dichlorohydrine and can under normal pressure, be carried out, and also can carry out adding to depress.The method of rectification and purification is to well known to a person skilled in the art method.
The catalyzer that the present invention is used for glycerol hydrochlorination production dichlorohydrine is a gac class catalyzer, and gac can directly use after drying, also can pass through modification and handle the back use.
The modifying method of activated carbon that the present invention adopts is to adopt properties-correcting agent such as ydrogen peroxide 50, sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid that gac is handled.
Described glycerol hydrochlorination is produced the method for dichlorohydrine, wherein the specific surface area of gac or modified activated carbon 500m at least
2/ g, pore volume is 0.65cm at least
3/ g.
Described glycerol hydrochlorination is produced the method for dichlorohydrine, wherein is that granular gac or modified activated carbon are indefinite form, garden cylindricality, sphere, and is fibrous, cellular or tabular.
The modified activated carbon that the present invention adopts prepares through following method:
(1), gac is joined in properties-correcting agent ydrogen peroxide 50, sulfuric acid, hydrochloric acid, phosphoric acid or the nitric acid, the mass ratio of gac and properties-correcting agent is 1: 1～1: 20, also can add the deionized water dilution that equates with the properties-correcting agent quality again;
(2), with mixture heating up to 40～100 of step (1) ℃, under whipped state, keep 4～12h;
(3), stir to finish after, be cooled to room temperature, with deionized water wash to neutral;
(4), behind 80～120 ℃ of following vacuum-drying 5～10h, obtain required catalyzer.
The manufacturing source of the used gac of the present invention is not limit; Can be timber, crop stalk, bamboo wood and processing waste thereof and shell; Also can be coal and oil and processed products thereof (comprising coal tar, coal-tar pitch, coal semicoke, petroleum hydrocarbon, petroleum residual oil, oil drop table, refinery coke etc.), and other types carbon raw material.The used gac of the present invention can be commercially available also can be homemade, the self-control process of active carbon is to well known to a person skilled in the art technology.
Gac of the present invention or modified activated carbon are powdery, granularity 280～80 mesh standard sieves; Perhaps be particulate state, granularity 80 orders～4 mesh standard sieves.。Granular gac comprises indefinite form, garden cylindricality, sphere, and fibrous, cellular, tabular etc., other shape gacs also are applicable to the present invention.
Catalyzer of the present invention is used for glycerol hydrochlorination and produces dichlorohydrine; The present invention has no particular limits the source and the purity of raw material glycerine; The source of glycerine can be the glycerine of a day chemical industry, Triple Pressed Stearic Acid production and production of biodiesel by-product, also can be the glycerine from biological fermentation and chemosynthesis, especially prepares the glycerine of biofuel institute by-product through greasy transesterification reaction; Be renewable resources, meet the requirement and the direction of contemporary chemical industry development.
Advantage of the present invention:
The gac class catalyzer of glycerine provided by the invention and hydrogenchloride chlorination production dichlorohydrine is a solid, and is active high, with the product separate easily, can be recycled.Have that technology is simple, the advantage of low production cost.
Embodiment
Further describe the present invention below in conjunction with embodiment, scope of the present invention is not limited to these embodiment.
Embodiment 1
Take by weighing commercially available 280～200 purpose ature of coal powdered carbons of 50g; Add the commercially available ydrogen peroxide 50 of 50g (the ydrogen peroxide 50 massfraction is 27%), be heated to 70 ℃, stir 12h; Cooled and filtered; With deionized water gac is washed till neutrality,, is put in the moisture eliminator subsequent use behind dry the end at 80 ℃ of following vacuum-drying 10h.The particle diameter of ydrogen peroxide 50 modified activated carbon does not change, and adopts the BET method to record specific surface area 500m
2/ g, pore volume 0.65m
3/ g.
Embodiment 2
Take by weighing the commercially available 200 purpose wood powder shaped activated carbons of 50g, add the commercially available concentrated hydrochloric acid of 200g (the hydrochloric acid massfraction is 36.5%), be heated to 60 ℃; Stir 6h, cooled and filtered is washed till neutrality with deionized water with gac; At 100 ℃ of following vacuum-drying 8h, be put in the moisture eliminator subsequent use behind dry the end.The particle diameter of concentrated hydrochloric acid modified activated carbon does not change, and adopts the BET method to record specific surface area 1000m
2/ g, pore volume 0.7m
3/ g.
Embodiment 3
Take by weighing the ature of coal columnar activated carbon of the commercially available diameter 1.5mm of 50g; Add the commercially available vitriol oil of 250g (the sulfuric acid massfraction is 98%), be heated to 60 ℃, stir 4h; Cooled and filtered; With deionized water gac is washed till neutrality,, is put in the moisture eliminator subsequent use behind dry the end at 100 ℃ of following vacuum-drying 6h.The particle diameter of vitriol oil modified activated carbon does not change, and adopts the BET method to record specific surface area 800m
2/ g, pore volume 0.7m
3/ g.
Embodiment 4
Take by weighing the commercially available 4-8 purpose of 50g coconut husk class granulated active carbon, add the commercially available phosphoric acid of 500g (the phosphoric acid quality mark is 98%), be heated to 80 ℃; Stir 8h, cooled and filtered is washed till neutrality with deionized water with gac; At 100 ℃ of following vacuum-drying 8h, be put in the moisture eliminator subsequent use behind dry the end.The particle diameter of phosphoric acid modification gac does not change, and adopts the BET method to record specific surface area 1500m
2/ g, pore volume 0.85m
3/ g.
Embodiment 5
Take by weighing the commercially available 20-40 purpose of 50g bamboo matter granulated active carbon, add the commercially available HNO of 1000g
3(the nitric acid massfraction is 65%) is heated to 40 ℃, stirs 4h, and cooled and filtered is washed till neutrality with deionized water with gac, at 120 ℃ of following vacuum-drying 5h, is put in the moisture eliminator subsequent use behind dry the end.The particle diameter of concentrated nitric acid modified activated carbon does not change, and adopts the BET method to record specific surface area 950m
2/ g, pore volume 0.8m
3/ g.
Embodiment 6
Coconut husk is pulverized, sieved, get particle diameter at 10～20 purpose raw material 40g, 120 ℃ of vacuum-dryings 8 hours.Put into 30g phosphoric acid again, under whipped state, soak 24h, the solid materials after the underpressure distillation must contain the coconut shell flour of phosphoric acid 120 ℃ of vacuum-dryings 8 hours.In the protection of the stream of nitrogen gas of 100ml/min down, be heated to 400 ℃ from room temperature with the temperature rise rate of 10 ℃/min, be incubated 2h after; Be heated to 900 ℃ with same stream of nitrogen gas and temperature rise rate again; Insulation 1h stops heating cooling back and takes out, and pulverizes the back again and crosses 200 mesh sieves; Promptly get coconut shell flour shaped activated carbon catalyzer, adopt the BET method to record specific surface area 1800m
2/ g, pore volume 0.9m
3/ g.
Embodiment 7
In having the reactor drum that stirs with water segregator capable, the activated-carbon catalyst that the adding commercially available glycerine of 100g and 0.5g embodiment 1 are prepared is heated to 120 ℃; Feed hydrogen chloride gas, the flow of hydrogen chloride gas is 300mL/min, reaction 24h; After reaction finishes; The liquid quality that slips out that from water trap, obtains is 86.1g, and the chlorated liquid quality that from reactor drum, obtains is 88.2g, and gas chromatographic analysis shows glycerol conversion yield 100%; Calculating a propylene chlorohydrin yield is 11.4%, and the dichlorohydrine yield is 87.9%.
Embodiment 8
In having the reactor drum that stirs with water segregator capable, the activated-carbon catalyst that the adding commercially available glycerine of 100g and 30g embodiment 2 are prepared is heated to 80 ℃; Feed hydrogen chloride gas, the flow of hydrogen chloride gas is 300mL/min, reaction 24h; After reaction finishes; The liquid quality that slips out that from water trap, obtains is 97.3g, and the chlorated liquid quality that from reactor drum, obtains is 77.2g, and gas chromatographic analysis shows glycerol conversion yield 100%; Calculating a propylene chlorohydrin yield is 10.7%, and the dichlorohydrine yield is 88.6%.
Embodiment 9
In having the reactor drum that stirs with water segregator capable, the activated-carbon catalyst that the adding commercially available glycerine of 100g and 10g embodiment 3 are prepared is heated to 180 ℃; Feed hydrogen chloride gas, the flow of hydrogen chloride gas is 1500mL/min, reaction 3h; After reaction finishes; The liquid quality that slips out that from water trap, obtains is 80.3g, and the chlorated liquid quality that from reactor drum, obtains is 88.5g, and gas chromatographic analysis shows glycerol conversion yield 99.3%; Calculating a propylene chlorohydrin yield is 23.5%, and the dichlorohydrine yield is 74.9%.
Embodiment 10
In having the reactor drum that stirs with water segregator capable, the activated-carbon catalyst that the adding commercially available glycerine of 100g and 5g embodiment 4 are prepared is heated to 140 ℃; Feed hydrogen chloride gas, the flow of hydrogen chloride gas is 50mL/min, reaction 80h; After reaction finishes; The liquid quality that slips out that from water trap, obtains is 99.6g, and the chlorated liquid quality that from reactor drum, obtains is 77.4g, and gas chromatographic analysis shows glycerol conversion yield 100%; Calculating a propylene chlorohydrin yield is 2.5%, and the dichlorohydrine yield is 95.8%.
Embodiment 11
In the reactor drum that has stirring and water segregator capable, adding commercially available glycerine of 100g and 10g embodiment 6 are prepared, are heated to 120 ℃; Feed hydrogen chloride gas, the flow of hydrogen chloride gas is 300mL/min, reaction 12h; After reaction finished, the liquid quality that slips out that from water trap, obtains was 93.4g, and the chlorated liquid quality that from reactor drum, obtains is 77.9g; Gas chromatographic analysis shows glycerol conversion yield 99.8%, and calculating a propylene chlorohydrin yield is 18.4%, and the dichlorohydrine yield is 80.6%.
Embodiment 12
In having the reactor drum that stirs with water segregator capable, the activated-carbon catalyst that the adding commercially available glycerine of 100g and 30g embodiment 5 are prepared is heated to 130 ℃; Feed hydrogen chloride gas, the flow of hydrogen chloride gas is 250mL/min, reaction 30h; After reaction finishes; The liquid quality that slips out that from water trap, obtains is 98.5g, and the chlorated liquid quality that from reactor drum, obtains is 77.3g, and gas chromatographic analysis shows glycerol conversion yield 100%; Calculating a propylene chlorohydrin yield is 7.8%, and the dichlorohydrine yield is 91.6%.
Embodiment 13
The catalyzer that obtains is filtered in embodiment 12 reactions to be recycled; The add-on of raw material glycerine; The flows of hydrogenchloride etc. are identical with embodiment 12, and temperature of reaction is also identical with embodiment 12 with the time, and the catalyzer that reaction end after-filtration obtains continues to reuse according to embodiment 12; Catalyzer accumulative total cycle repeats is used 5 times, and the glycerol conversion yield of each repeated experiments is the yield of 100%, one propylene chlorohydrin and dichlorohydrine and sees table 1.
Table 1
| Cycle index | 1 | 2 | 3 | 4 | 5 |
| Dichlorohydrine yield/% | 8.2 | 8.1 | 7.6 | 7.9 | 8.2 |
| Dichlorohydrine yield/% | 91.3 | 91.6 | 91.9 | 91.5 | 91.2 |
Claims (9)
1. the method that glycerol hydrochlorination is produced dichlorohydrine is characterized in that glycerine and hydrogenchloride under gac class catalyst action, under 80～180 ℃, and the method that reaction 3～80h produces dichlorohydrine.
2. glycerol hydrochlorination according to claim 1 is produced the method for dichlorohydrine, it is characterized in that catalyzer uses the gac of gac or process modification.
3. glycerol hydrochlorination according to claim 2 is produced the method for dichlorohydrine, it is characterized in that modifying method of activated carbon is to adopt ydrogen peroxide 50, sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid that gac is handled.
4. glycerol hydrochlorination according to claim 2 is produced the method for dichlorohydrine, and the specific surface area that it is characterized in that gac or modified activated carbon is 500m at least
2/ g, pore volume is 0.65cm at least
3/ g.
5. glycerol hydrochlorination according to claim 2 is produced the method for dichlorohydrine, it is characterized in that gac or modified activated carbon are powdery, granularity 280～80 mesh standard sieves; Perhaps be particulate state, granularity 80 orders～4 mesh standard sieves.
6. glycerol hydrochlorination according to claim 5 is produced the method for dichlorohydrine, it is characterized in that particulate state comprises indefinite form, garden cylindricality, sphere, and is fibrous, cellular or tabular.
7. glycerol hydrochlorination according to claim 2 is produced the method for dichlorohydrine, it is characterized in that the modified activated carbon preparation method comprises the steps:
(1), gac is joined in properties-correcting agent ydrogen peroxide 50, sulfuric acid, hydrochloric acid, phosphoric acid or the nitric acid, the mass ratio of gac and properties-correcting agent is 1: 1～1: 20, also can add the deionized water dilution that equates with the properties-correcting agent quality again;
(2), with mixture heating up to 40～100 of step (1) ℃, under whipped state, keep 4～12h;
(3), stir to finish after, be cooled to room temperature, with deionized water wash to neutral;
(4), at 80～120 ℃ of following vacuum-drying 5～10h.
8. glycerol hydrochlorination according to claim 1 is produced the method for dichlorohydrine, it is characterized in that catalyst levels is 0.5～30% of qualities of glycerin in mass.
9. glycerol hydrochlorination according to claim 1 is produced the method for dichlorohydrine, and the flow that it is characterized in that hydrogenchloride is 0.5～15mL/ (ming
Glycerine).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110412413.7A CN102491877B (en) | 2011-12-12 | 2011-12-12 | Method for producing dichlorhydrin by means of glycerin hydrochlorination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110412413.7A CN102491877B (en) | 2011-12-12 | 2011-12-12 | Method for producing dichlorhydrin by means of glycerin hydrochlorination |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102491877A true CN102491877A (en) | 2012-06-13 |
| CN102491877B CN102491877B (en) | 2015-02-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103111326A (en) * | 2013-03-11 | 2013-05-22 | 南京工业大学 | Carboxylic acid group functionalization SBA molecular sieve based catalyst for synthesizing dichloropropanol through glycerol hydrochlorination |
| 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 |
| CN104926666A (en) * | 2015-03-29 | 2015-09-23 | 安徽同丰橡塑工业有限公司 | Production process of rubber anti-aging agent |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103111326A (en) * | 2013-03-11 | 2013-05-22 | 南京工业大学 | Carboxylic acid group functionalization SBA molecular sieve based catalyst for synthesizing dichloropropanol through glycerol hydrochlorination |
| 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 |
| CN103464178B (en) * | 2013-07-09 | 2015-03-25 | 南京奥凯化工科技有限公司 | AG-01 catalyst used for synthesis of dichloropropanol by chlorination of glycerin |
| CN104926666A (en) * | 2015-03-29 | 2015-09-23 | 安徽同丰橡塑工业有限公司 | Production process of rubber anti-aging agent |
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| CN102491877B (en) | 2015-02-04 |
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