CN104591967B - The process of crude glycerine and its application in epoxychloropropane produces - Google Patents
The process of crude glycerine and its application in epoxychloropropane produces Download PDFInfo
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- CN104591967B CN104591967B CN201310746633.2A CN201310746633A CN104591967B CN 104591967 B CN104591967 B CN 104591967B CN 201310746633 A CN201310746633 A CN 201310746633A CN 104591967 B CN104591967 B CN 104591967B
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- glycerol
- crude glycerine
- hydrogen chloride
- water
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 854
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 342
- 238000000034 method Methods 0.000 title claims abstract description 98
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 230000008569 process Effects 0.000 title claims abstract description 56
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 85
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 85
- 239000007789 gas Substances 0.000 claims abstract description 49
- 238000003672 processing method Methods 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 91
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 claims description 59
- 238000002360 preparation method Methods 0.000 claims description 34
- 238000012545 processing Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 241001597008 Nomeidae Species 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 38
- 235000002639 sodium chloride Nutrition 0.000 description 33
- 238000005660 chlorination reaction Methods 0.000 description 28
- 239000002956 ash Substances 0.000 description 24
- 239000011780 sodium chloride Substances 0.000 description 19
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 17
- 239000012535 impurity Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000004821 distillation Methods 0.000 description 13
- 150000002924 oxiranes Chemical class 0.000 description 10
- 241001550224 Apha Species 0.000 description 9
- -1 acetate propylene ester Chemical class 0.000 description 8
- 235000009508 confectionery Nutrition 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 238000010612 desalination reaction Methods 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000007363 ring formation reaction Methods 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000003225 biodiesel Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- ZXCYIJGIGSDJQQ-UHFFFAOYSA-N 2,3-dichloropropan-1-ol Chemical compound OCC(Cl)CCl ZXCYIJGIGSDJQQ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical class OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 235000019737 Animal fat Nutrition 0.000 description 1
- YWNYZQTZOONLGU-UHFFFAOYSA-N C(CC)Cl.[O] Chemical compound C(CC)Cl.[O] YWNYZQTZOONLGU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical class NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/94—Use of additives, e.g. for stabilisation
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
The present invention relates to the process of crude glycerine and its application in epoxychloropropane produces.The present invention relates to a kind of crude glycerine processing method, methods described comprises the steps：（a）It is passed through hydrogen chloride gas in crude glycerine, separate out insoluble solid；（b）Remove the solid separating out, glycerol after being processed by filtering.
Description
Technical field
A kind of the present invention relates to processing method of crude glycerine, and the side using glycerol production epoxychloropropane after processing
Method.
Background technology
Epoxychloropropane is to produce epoxy resin, chlorohydrin rubber, stabilizer, surfactant, fire retardant and oilfield chemistry
The important source material of the products such as product, and dichlorohydrin is the key intermediate of its synthesis.At present, the industrial side producing dichlorohydrin
Method, the propylene high-temperature chloridising predominantly with propylene as raw material and acetate propylene ester process.Propylene high-temperature chloridising exist high energy consumption,
The problems such as propylene utilization rate is low, by-product is many and chlorine-contained wastewater discharge capacity is too big；Acetate propylene ester process exist process route length,
Invest the problems such as big, expensive catalyst and short life.Generally speaking, above two commercial run all consumes non-renewable money in a large number
Source, but also consume chlorine in a large number, cause serious environmental pollution.Since entering 21st century, due to countries in the world energetically
Development biodiesel, therewith can a large amount of glycerol of by-product, cause glycerol market superfluous, so that glycerol price is slumped, under this background,
Many countries have developed the new technology with glycerol for raw material production epoxychloropropane.
The technique of glycerol method synthesizing epoxy chloropropane is related to two committed steps：（1）Glycerol is made in catalyst with hydrogen chloride
Generate dichlorohydrin with lower reaction；（2）Dichlorohydrin carries out cyclization in the alkaline solution such as sodium hydroxide or lime cream and obtains
To epoxychloropropane.Because cyclization process is similar, relative maturity, so people are concentrated mainly on research glycerol and chlorine
Change the method that hydrogen is synthesized dichlorohydrin.
Have the method by glycerol and hcl reaction synthesizing dichloropropanol for many patent literatures.It can be found that this
In a little patents, glycerol used is primarily referred to as glycerol more than 95% for the content, such as China Forestry Science Research Institute（CN
101003523 A）Catalytic chlorination glycerol is 95% industry glycerol, Spolek of Czech（CN
1845888 A, WO 2005021476）Use 97.5% glycerol, Yanzhou Tian Cheng Chemical Co., Ltd.（CN 101704722A）With
99.5% smart glycerol, Italian Ah Purcell Co., Ltd.（CN 101184715A, WO2006111810）Use 99.9% anhydrous glycerol.
The above patent literature be all using high-purity glycerol not using crude glycerine for raw material main cause have following several
Point：（1）In the continuous chlorination production process of glycerol, the residual liquid that the inorganic salt in crude glycerine can be produced with chlorination mixes,
Easily lump, cause the blocking of pipeline, need periodically to carry out pipe-dredging, not only taken but also effort, and reduced production capacity, impact produces
Normal operation；（2）Inorganic salt in crude glycerine can enter the dichlorohydrin vacuum distillation stage, causes distillation system to bubble, impact
Steam the quality of dichlorohydrin.If being processed to crude glycerine and purification, obtain carrying out the glycerol of chlorination reaction, you can fall
Low cost, additional income.
The method of conventional purifying crude glycerol is distillation under vacuum, and U.S. patent documents US 4655879 are in purifying crude glycerol
During, pretreated crude glycerine is carried out vacuum distillation in thin layer evaporator.This needs careful control condition,
Because when heating-up temperature reaches 170-180 DEG C, glycerol can decompose or be polymerized, and lead to the formation of impurity and reduce returning of glycerol
Yield.
In order to stablize still-process, and the qualities of glycerin after vacuum distillation can be improved, Russ P RU2210560 is subtracting
The auxiliary agent Fenozean28 of 0.2-0.3% content is added, effect is improved in the forward direction glycerol of pressure distillation, but by subtracting
Pressure way of distillation purifying crude glycerol is not fee from the distillation equipment of costliness, leads to higher production cost.
Ion exchange also has important application in sweet oil handling.Jiangmen City Hongjie Fine Chemical Co., Ltd（CN
101475444A）Purification is carried out to crude glycerine by ion-exchange-resin process, method be crude glycerine is filtered after be evaporated
Moisture removal and methanol；Carried out ion exchange again and removed inorganic salt；Obtain purity finally by membrane distillation sweet more than 95%
Oil.
Patent WO 2008156612 methods described include continuously two or more nanofiltration system or reverse osmosis filter to thick
Glycerol mixture is filtered, and at least one filter membrane comprises the filter medium that contact angle is about 44-56 degree.
French sieve ground is sub-（CN 102596871 A, WO 2011030204）Purification is carried out to crude glycerine by chemical treatment,
It is divided into four steps：（1）By crude glycerine and low-grade carboxylic acid or anhydride reaction；（2）The glyceride being formed by separated；（3）By shape
The ester becoming is reacted with least one alkylol or cycloalkyl alcohol；（4）Separate and form smart glycerol, high purity 99%, but the method
Complex steps are it is difficult to industrialization.
French sieve ground is sub-（CN 103097327, WO 2012034904）Also disclosed thick by organic solvent purification by liquid extraction
The method of glycerol, is divided into four steps：（1）By crude glycerine and suitable immiscible organic solvent；（2）Separate soluble phase and liquid phase；（3）
Remove the solvent in liquid phase after separating and moisture；（4）Reclaim glycerol, by glycerol content 79.3%, water content 15.8% and salt content
1.61% crude glycerine purifies to the smart glycerol that glycerol content is 97.5%.But it is big to there is consumption of organic solvent in the method, energy consumption
Big the shortcomings of, it is not suitable for industrial application.
Belgian Solvay（CN 101066909 A,WO 2007144335）Disclose one kind and contain glycerol alkyl
The purification process of ether crude glycerine, and the method using glycerol synthesizing dichloropropanol after purification.This crude glycerine can be dense by evaporating
Contracting, evaporative crystallization, distillation, fractional distillation, at least one of air stripping or liquid-liquid extraction method is processed, and these processing methods make dichlorohydrin
Production method complicate.
In view of existing crude glycerine treatment technology, need to develop that a kind of operating procedure is few, expense is relatively low, temperature and pressure
The crude glycerine processing method of condition milder, especially from the crude glycerine of by-products a large amount of during production of biodiesel, through place
Can be used as the cheap raw material of synthesizing epoxy chloropropane after reason.
Content of the invention
Problems to be solved by the invention
It is an object of the invention to provide a kind of simple crude glycerine processing method, and prepare epoxy using glycerol after processing
The method of chloropropane.
The raw material of the epoxychloropropane of glycerin chlorination production at present is the glycerol of more than 95% purity, and the glycerol of 95% purity
It is all by obtaining crude glycerine high temperature distillation, wherein deriving from the crude glycerine of biodiesel byproduct, in addition to containing glycerol, also
Containing water, slaine and other Organic substances on a small quantity, will certainly there is partial glycerol polymerization when it is distilled, decompose etc. and making
Glycerol yield is relatively low, and distillation column bottom can by-product color be gathered compared with the deep and glycerol of the relatively low a large amount of saliferous of value and glycerol
Compound.If directly crude glycerine is applied to glycerin chlorination to produce dichlorohydrin, the above-mentioned listed impurity in crude glycerine can be to thick
Glycerin chlorination produces a very large impact.The presence of particularly sodium chloride, can be to glycerin chlorination production equipment line clogging it is impossible to carry out
Normal production, therefore needs crude glycerine is processed before chlorination.
For solution to problem
[1] the present invention relates to a kind of crude glycerine processing method, the method comprises the steps：
（a）Crude glycerine is contacted with hydrogen chloride gas, is separated out insoluble solid；
（b）The described solid separating out, glycerol after being processed are removed by solid-liquid separation.
[2] the present invention relates to a kind of crude glycerine processing method is it is characterised in that the method comprises the steps：
（a）Crude glycerine is removed at least a portion water, obtains crude glycerine after eliminating water；
（b）Crude glycerine after described eliminating water is contacted with hydrogen chloride gas, separates out insoluble solid；
（c）The described solid separating out, glycerol after being processed are removed by solid-liquid separation.
[3] the crude glycerine processing method according to [1] or [2], wherein step（a）In crude glycerine comprise 5 weight % extremely
The glycerol of 95 weight %, the water of 1 weight % to 80 weight %, and 1 weight % is to the slaine of 30 weight %.
[4] the crude glycerine processing method according to [1], wherein step（b）5 are comprised in glycerol after the described process obtaining
Weight % to 90 weight % glycerol, the hydrogen chloride of 5 weight % to 40 weight %, the water of 0.5 weight % to 60 weight %, and be less than 1 weight
The slaine of amount %.
[5] the crude glycerine processing method according to [2], wherein step（a）Wrap in crude glycerine after the described eliminating water obtaining
Glycerol containing 30 weight % to 99 weight %, the water of 0.1 weight % to 10 weight %, and 1 weight % is to the slaine of 55 weight %.
[6], according to the crude glycerine processing method described in [1], when being wherein passed through hydrogen chloride gas, the gauge pressure of system is-
0.1MPa to 1MPa, the described amount being passed through hydrogen chloride is the 5% to 70% of crude glycerine weight, described contact with hydrogen chloride gas thick
The initial temperature of glycerol is 20 DEG C to 200 DEG C, and in solid-liquid separation, crude glycerine temperature is 20 DEG C to 200 DEG C.
[7], according to the crude glycerine processing method described in [2], when being wherein passed through hydrogen chloride gas, the gauge pressure of system is-
0.1MPa to 1MPa, the described amount being passed through hydrogen chloride is 5% to 70% of crude glycerine weight after eliminating water, described connects with hydrogen chloride gas
After tactile eliminating water the initial temperature of crude glycerine be 20 DEG C to 200 DEG C, after the eliminating water in solid-liquid separation crude glycerine temperature be 20 DEG C extremely
200℃.
[8] the crude glycerine processing method according to [2], wherein step（c）Comprise in glycerol after the described process obtaining
The glycerol of 50 weight % to 95 weight %, the hydrogen chloride of 1 weight % to 30 weight %, the water of 0.1 weight % to 20 weight %, and it is less than 1
The slaine of weight %.
[9] a kind of preparation method of epoxychloropropane is it is characterised in that the method comprises the steps：
（a）Glycerol after being processed using the method described in any one of [1-8]；
（b）In the presence of carboxylic acidss catalyst, by step（a）Glycerol or its mixture and chlorine after the described process obtaining
Change hydrogen precursor reactant, prepare dichlorohydrin；
（c）Dichlorohydrin and cyclizing agent are carried out removing hcl reaction, prepares epoxychloropropane.
[10] preparation method according to the epoxychloropropane described in [9], wherein, described carboxylic acidss catalyst is acetic acid, third
The combination of one or more of diacid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, Azelaic Acid and decanedioic acid.
[11] preparation method of the epoxychloropropane according to [9], wherein, the consumption of described carboxylic acidss catalyst is place
The 0.1% to 10% of glycerol mole after reason, preferably 1% to 6%.
[12] preparation method of the epoxychloropropane according to [9], wherein, step（b）Reaction temperature be 80 DEG C extremely
130 DEG C, preferably 100 DEG C to 120 DEG C.
[13] preparation method of the epoxychloropropane according to [9], wherein, step（b）Response time be 1h extremely
20h, preferably 5h to 15h.
[14] preparation method of the epoxychloropropane according to [9], wherein, step（b）Glycerol and chlorination after middle process
The mol ratio of hydrogen is 1:2 to 1:5, preferably 1:2 to 1:3.
[15] preparation method of the epoxychloropropane according to [9], wherein, step（b）The water of middle formation, hydrogen chloride and
Dichlorohydrin vacation ternary azeotrope removes from reaction system and obtains carry-over, in step（b）Reaction terminate after, by decompression
Dichlorohydrin is steamed and obtains steaming thing by distillation.
[16] preparation method of the epoxychloropropane according to [9], wherein, described carry-over is mixed with steaming thing
To dichloropropanol mixture, and prepare epoxychloropropane for cyclization.
[17] preparation method of the epoxychloropropane according to [9], wherein, step（b）The dichlorohydrin obtaining comprises
1,3- dichlorohydrin and 2,3- dichlorohydrin.
[18] preparation method of the epoxychloropropane according to [9], wherein, the concentration of described dichlorohydrin, based on two
Chloropropyl alcohol mixture total weight gauge, is 10 weight % to 95 weight %, preferably 60 weight % are to 90 weight %.
[19] preparation method of the epoxychloropropane according to [9], wherein, step（c）Cyclizing agent be sodium hydroxide
Solution or lime cream, preferably sodium hydroxide solution.
[20] preparation method of the epoxychloropropane according to [9], wherein, step（c）Cyclisation agent concentration, be 1 weight
Amount % to 75 weight %, preferably 10 weight % to 55 weight %, more preferably 20 weight % to 40 weight %, particularly preferred 20 weight % to 30
Weight %.
[21] preparation method according to the epoxychloropropane described in [9], wherein, described dichlorohydrin and cyclizing agent mole
Than for 1:1 to 1:3, preferably 1:1 to 1:1.5.
[22] preparation method according to the epoxychloropropane described in [9], wherein, described cyclization temperature is for 20 DEG C extremely
100 DEG C, preferably 50 DEG C to 90 DEG C.
[23] a kind of glycerin compositions, wherein comprise 5 weight % to the glycerol of 90 weight %, the chlorine of 5 weight % to 40 weight %
Change hydrogen, the water of 0.5 weight % to 60 weight %, and the slaine less than 1 weight %, preferred glycerin compositions contain 50 weight % extremely
The glycerol of 90 weight %, the hydrogen chloride of 5 weight % to 30 weight %, the water of 1 weight % to 20 weight %, it is less than 1 more than 0.02 weight %
The slaine of weight %.
[24] a kind of method preparing epoxide and its derivant, wherein, using claim 1 and claim 2
Method process the glycerol that obtains and be prepared as initiation material.
The effect of invention
Compared with the method for application in epoxychloropropane production with existing crude glycerine processing method and glycerol, the present invention has
Have the following advantages：
（1）The cost of crude glycerine raw material is far below the glycerol of more than 95% content, and the production that epoxychloropropane is greatly reduced becomes
This；
（2）Crude glycerine is directly used in production epoxychloropropane after processing, and passes through distillation compared to crude glycerine and obtains 95% glycerol
Carry out again producing for epoxychloropropane, no polyglycerine produces, the utilization rate of glycerol improves further, reduce life further
Produce cost；
（3）Operation is simple for the process of crude glycerine, and process conditions include temperature, pressure milder；
（4）The process energy consumption of crude glycerine is little, processing cost is low, be easily achieved industrialization；
（5）Hydrogen chloride in glycerol after process can be used for chlorination reaction as raw material, realizes recycling, energy-saving ring
Protect；
（6）After process, the chlorination effect of glycerol is suitable with the chlorination effect of content more than 95% glycerol.
Specific embodiment
The invention provides a kind of crude glycerine processing method, the method comprises the steps：
（a）Crude glycerine is contacted with hydrogen chloride gas, is separated out insoluble solid；
（b）The described solid separating out, glycerol after being processed are removed by solid-liquid separation.
The invention provides a kind of crude glycerine processing method, the method comprises the steps：
（a）Crude glycerine is removed at least a portion water, obtains crude glycerine after eliminating water；
（b）Crude glycerine after described eliminating water is contacted with hydrogen chloride gas, is separated out insoluble solid；
（c）The described solid separating out, glycerol after being processed are removed by solid-liquid separation.
Wherein said crude glycerine and the way of contact of hydrogen chloride include spraying, countercurrently, vapour-liquid mix, leads to in crude glycerine
Enter the modes such as hydrogen chloride gas, what those skilled in the art understood fully can be mixed crude glycerine with hydrogen chloride gas
The embodiment closing all can apply in the present invention.
Wherein said insoluble solid includes the solid existing with granule or suspended state, including slaine.At this
In a bright embodiment, described insoluble solid refers to solid metal salt, and slaine is selected from alkali metal salt or alkaline earth gold
Belong to salt.
Wherein the mode removing at least a portion water in crude glycerine is included vacuum distillation, air-distillation, drying, adsorbent
The modes such as absorption.The mode that those skilled in that art may be appreciated moisture in deglycerizin all can be applicable in the present invention.
Present invention also offers a kind of glycerin compositions, the wherein glycerol containing 50 weight % to 90 weight %, 5 weight % are extremely
The hydrogen chloride of 30 weight %, the water of 1 weight % to 60 weight %, it is less than the slaine of 1 weight % more than 0.02 weight %.This glycerol can
Prepare dichlorohydrin to be directly used in, and do not need further to process.Due to having contained portion in the glycerol that obtains after processing
Divide hydrogen chloride gas, hydrogen chloride can be passed through therefore during preparing dichlorohydrin less.
Present invention also offers a kind of method preparing epoxide and its derivant, wherein, obtained using said method
The glycerol arriving is as initiation material.
In the method according to the invention, epoxide includes epoxychloropropane etc., and epoxides refer in epoxy
Further reacted on the basis of compound, using having that the conventional method such as the replacement of functional group, grafting, polymerization obtains
Machine thing, is caned including epoxide and is directly or indirectly reacted the compound obtaining.
Epoxides are typically selected from epoxy resin, (+)-2,3-Epoxy-1-propanol ethers, (+)-2,3-Epoxy-1-propanol esters, glycidyl amides
Class, glycidyl imides, (+)-2,3-Epoxy-1-propanol amine.Described epoxides also include carrying out various changing to these compounds
The alternate compounds obtaining after property.Described epoxides can serve as coagulating agent class, wet strengthening resin class, cationics
Class, fire retardant class, for cleaning agent composition product, epichlorohydrin elastomer class, the polyether-polyols of halogenation.System
The method of standby above-mentioned epoxide and epoxides is all known as is known to those skilled in the art, refers to corresponding work
Tool book or textbook.
In an embodiment of the invention, wherein said method comprises the steps：It is passed through chlorine in crude glycerine (A)
Change hydrogen, gradually precipitating metal salt, remove the slaine separating out, glycerol after being processed finally by Filter Press
(C1).
In yet another embodiment of the present invention, wherein said method comprises the steps：Crude glycerine (A) is subtracted
Pressure distillation removes most of moisture therein and low-boiling-point organic compound, obtains crude glycerine (B) after eliminating water, then slightly sweet to after eliminating water
It is passed through hydrogen chloride gas in oily (B), gradually precipitating metal salt, remove, finally by Filter Press, the slaine separating out, obtain
Glycerol (C2) after process.
In the present invention, the embodiment of crude glycerine processing method can be intermittently operated or continuous operation, preferably continuously grasps
Make.
Intermittently operated refers in the processing procedure of crude glycerine, crude glycerine batch processing, and often a collection of crude glycerine all leads to respectively
Cross eliminating water, be passed through glycerol after the operation such as hydrogen chloride gas, filter pressing desalination is processed.
Continuous operation refers in the processing procedure of crude glycerine, and crude glycerine continuous processing is continuously passed through crude glycerine, continuously
Through eliminating water, it is passed through glycerol after the operation such as hydrogen chloride gas, filter pressing desalination is processed.
Wherein, described slaine is metal chloride or metal sulfate, preferably be selected from sodium chloride, potassium chloride or sodium sulfate,
Potassium sulfate.Described hydrogen chloride gas are derived from combustion method or prepare the by-product producing in Organic substance, in the industrial production
The hydrogen chloride gas in source are used equally in the present invention.Described hydrogen chloride gas can include less than 5% water vapour, preferably
Less than 3% water vapour.
Wherein, described crude glycerine (A) refers to that natural oil industrial process, such as saponification, highly pressured hydrolysis or the ester with alcohol are handed over
Change the glycerol that reaction obtains, particularly preferably produce, from vegetable oil and Animal fat, the crude glycerine obtaining biodiesel process.
Crude glycerine used herein can pass through commercially available, as bought in Wilmar Trading Pte Ltd company
Arrive.
In the present invention, term " solid-liquid separation " refers to using solid-liquid separation such as standing, filter pressing, sucking filtration, or centrifugations
Means make solid and liquid be separated.
Wherein, described crude glycerine (A) comprises 5 weight % to the glycerol of 95 weight %, preferably 40 weight % to 90 weight % sweet
Oil, the glycerol of more preferably 70 weight % to 90 weight %.Described crude glycerine (A) comprises 1 weight % to the water of 80 weight %, preferably 5 weights
The water of amount % to 30 weight %, the water of more preferably 5 weight % to 20 weight %.
Wherein, based on crude glycerine total amount meter, the ash of described crude glycerine (A) is less than 35 weight %, preferably smaller than 15 weights
Amount %, more preferably less than 5 weight %.The ash of described crude glycerine (A) is essentially from slaine.Described crude glycerine (A) comprises 1 weight
The slaine of amount % to 30 weight %, the slaine of preferably 1 weight % to 15 weight %, the metal of more preferably 1 weight % to 5 weight %
Salt.
Wherein, the temperature when being passed through hydrogen chloride gas for the described crude glycerine (A) is 20 DEG C to 200 DEG C, preferably 30 DEG C to 150
DEG C, more preferably 40 DEG C to 100 DEG C.Be passed through in described crude glycerine (A) hydrogen chloride gas amount be crude glycerine (A) weight 5% to
70%, preferably 8% to 50%, more preferably 10% to 37%.Described crude glycerine (A) when being passed through hydrogen chloride gas, the gauge pressure of system is-
0.1MPa to 1MPa, preferably 0.01MPa to 0.5MPa, more preferably 0.01MPa to 0.1MPa.
Wherein, during described filter pressing, the filter cloth aperture of pressure filter is 40 mesh to 1250 mesh, preferably 100 mesh to 800 mesh, more preferably
500 mesh are to 800 mesh.After process during described solid-liquid separation glycerol temperature be 20 DEG C to 200 DEG C, preferably 30 DEG C to 150 DEG C, more excellent
Select 40 DEG C to 100 DEG C.
Wherein, 5 weight % are comprised to the glycerol of 90 weight % in glycerol (C1) after described process, preferably 40 weight % are to 80 weights
The glycerol of amount %, the glycerol of more preferably 60 weight % to 80 weight %.5 weight % are comprised to 40 weights in glycerol (C1) after described process
The hydrogen chloride of amount %, the hydrogen chloride of preferably 5 weight % to 30 weight %, the hydrogen chloride of more preferably 10 weight % to 20 weight %.Described place
1 weight % is comprised to the water of 60 weight %, the water of preferably 5 weight % to 30 weight %, more preferably 5 weight % are extremely in glycerol (C1) after reason
The water of 15 weight %.
Wherein, based on glycerol total amount meter after processing, after described process, the ash of glycerol (C1) is less than 2 weight %, preferably little
In 1 weight %, more preferably less than 0.5 weight %.After described process, the ash of glycerol (C1) is essentially from slaine.After described process
In glycerol (C1), the content of slaine is less than 1 weight %, preferably smaller than 0.5 weight %, more preferably less than 0.3 weight %.
In yet another embodiment of the present invention, wherein, 30 weight % are comprised in crude glycerine (B) after described eliminating water to 99
The glycerol of weight %, the glycerol of preferably 60 weight % to 95 weight %.0.1 weight % is comprised to 20 in crude glycerine (B) after described eliminating water
The water of weight %, the water of preferably 0.5 weight % to 10 weight %, the water of more preferably 0.5 weight % to 5 weight %.Slightly sweet after described eliminating water
Oily (B) comprises 0.5 weight % to the slaine of 55 weight %, the slaine of preferably 1 weight % to 30 weight %, and more preferably 1 weight % is extremely
The slaine of 15 weight %.
Wherein, when being passed through hydrogen chloride gas, after described eliminating water the initial temperature of crude glycerine (B) be 20 DEG C to 200 DEG C, excellent
Select 30 DEG C to 150 DEG C, more preferably 40 DEG C to 100 DEG C.Be passed through in the crude glycerine (B) to after described eliminating water hydrogen chloride gas amount be except
The 5% to 70% of crude glycerine (B) weight after water, preferably 8% to 50%, more preferably 10% to 37%.In the crude glycerine (B) to after described eliminating water
In when being passed through hydrogen chloride gas, system gauge pressure is -0.1MPa to 1MPa, preferably 0.01MPa to 0.5MPa, more preferably 0.01MPa
To 0.1MPa.
Wherein, during described filter pressing, the filter cloth aperture of pressure filter is 40 mesh to 1250 mesh, preferably 100 mesh to 800 mesh, more preferably
500 mesh are to 800 mesh.After process during described solid-liquid separation glycerol temperature be 20 DEG C to 200 DEG C, preferably 30 DEG C to 150 DEG C, more excellent
Select 40 DEG C to 100 DEG C.
Wherein, 50 weight % are comprised to the glycerol of 95 weight % in glycerol (C2) after described process, preferably 70 weight % are to 95 weights
The glycerol of amount %, the glycerol of more preferably 70 weight % to 85 weight %.1 weight % is comprised to 30 weights in glycerol (C2) after described process
The hydrogen chloride of amount %, the hydrogen chloride of preferably 5 weight % to 20 weight %, the hydrogen chloride of more preferably 5 weight % to 15 weight %.Described place
0.1 weight % is comprised to the water of 20 weight %, the water of preferably 0.3 weight % to 8 weight %, more preferably 0.5 weight in glycerol (C2) after reason
The water of amount % to 5 weight %.Based on glycerol total amount meter after processing, after described process, the ash of glycerol (C2) is less than 2 weight %, excellent
Choosing is less than 1 weight %, more preferably less than 0.5 weight %.
Wherein, described process after glycerol (C2) ash essentially from slaine.Metal in glycerol (C2) after described process
The content of salt is less than 1%, preferably less than 0.5%, more preferably less than 0.3%.
On the other hand, the invention provides a kind of method preparing epoxychloropropane is it is characterised in that methods described adopts
Glycerol (C1) or (C2) after the process that above-mentioned crude glycerine processing method obtains, or glycerol (C1) and (C2) after the process of arbitrary proportion
Composition production epoxychloropropane, the method comprises the steps：
（1）In the presence of carboxylic acidss catalyst, glycerol (C1) or (C2) after processing, or sweet after the process of arbitrary proportion
Oily (C1) is reacted with hydrogen chloride gas with the compositionss of (C2), prepares dichlorohydrin；
（2）Dichlorohydrin and cyclizing agent are carried out removing hcl reaction, prepares epoxychloropropane.
Wherein, described process after glycerol (C1) or (C2), or the combining of glycerol (C1) and (C2) after the process of arbitrary proportion
The hydrogen chloride containing in thing can participate in reaction as raw material in dichlorohydrin preparation process.
Wherein, described carboxylic acidss catalyst is including acetic acid, malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, Azelaic Acid, the last of the ten Heavenly stems
The combination of one or more of the organic carboxyl acids such as diacid.Wherein, the consumption of described carboxylic acidss catalyst rubs for glycerol after processing
The 0.1% to 10% of that amount, preferably 1% to 6%.
Wherein, described step（1）Reaction temperature be 80 DEG C to 130 DEG C, preferably 100 DEG C to 120 DEG C.Wherein, described step
Suddenly（1）Response time be 1h to 20h, preferably 5h to 15h.Wherein, after described process, glycerol and the mol ratio of hydrogen chloride are 1:2
To 1:5, preferably 1:2 to 1:3.Wherein, described hydrogen chloride is dry hydrogen chloride gas.
Wherein, the water of formation, hydrogen chloride and dichlorohydrin vacation ternary azeotrope are removed from reaction system and referred to as take out of
Thing, step（1）Dichlorohydrin is steamed referred to as steaming thing by vacuum distillation after terminating by reaction.
Wherein, described carry-over and steaming thing are mixed to get dichloropropanol mixture, and prepare ring for cyclization
Oxygen chloropropane.Wherein, the product dichlorohydrin obtaining comprises 1,3- dichlorohydrin and 2,3- dichlorohydrin.Described dichlorohydrin
Concentration, based on dichloropropanol mixture gross weight meter, is 10 weight % to 95 weight %, preferably 50 weight % are to 90 weight %.
Wherein, step（2）Described in cyclizing agent be sodium hydroxide solution or lime cream（Calcium hydroxide）, preferably cyclizing agent is
Sodium hydroxide solution.Wherein, the concentration of described cyclizing agent is 1 weight % to 75 weight %, and preferably 10 weight % are to 55 weight %, more excellent
Select 20 weight % to 40 weight %, particularly preferred 20 weight % are to 30 weight %.Wherein, the mol ratio of described dichlorohydrin and cyclizing agent
For 1:1 to 1:3, preferably 1:1 to 1:1.5.Described cyclisation temperature is 20 DEG C to 100 DEG C, preferably 50 DEG C to 90 DEG C.
In the present invention, described term " crude glycerine " is the crude glycerine from biodiesel byproduct, and it is except containing sweet
Oil is outer, also contain water, slaine and other Organic substances on a small quantity.The presence of these materials can produce very big shadow to crude glycerine chlorination
Ring, therefore need crude glycerine is processed before chlorination.
In the present invention, described term " gauge pressure " is the fluid instruction pressure on the basis of local ambient atmosphere pressure, can
Recorded with piezometer, referred to as gauge pressure.I.e.：Gauge pressure=absolute pressure-ambient atmosphere pressure.Gauge pressure represents less than ambient air for negative value
Pressure, gauge pressure is higher than ambient atmosphere pressure on the occasion of expression.
Embodiment
The following examples are that the present invention is expanded on further, and it is only used for explaining and descriptive purpose, the present invention's
Content is not limited to this.Embodiment in description of the invention is only used for that the present invention will be described, and it is not to the present invention
Protection domain play restriction effect.Protection scope of the present invention is only defined by the claims, and those skilled in the art are at this
Any interpolation, replacement or the modification made on the basis of bright disclosed embodiment fall within protection scope of the present invention.
Wherein, unless otherwise indicated, " % " expression " weight % " in embodiment.
The assay method of crude glycerine index is：GB/T 13216-2008 is shown in content, moisture and determination of ash, and salt content is shown in
QB/T 2623.6-2003.
The assay method of epoxychloropropane leading indicator is：GB/T 13097- is shown in color and luster, content, moisture and density measurement
2007.
Dichloropropanol content is detected by GC method, and with reference to Jia Chaohui etc., gas chromatogram measures epoxy chlorine to detailed process simultaneously
Propane and its intermediate, fine-chemical intermediate, volume 38 phase in year the 3rd, in June, 2008,68-70 page of method.
Embodiment 1
The process of crude glycerine
Raw material crude glycerine is consisting of the following：80.6% glycerol, 14.3% water, 3.6% sodium chloride, balance of impurity；Wherein, base
In crude glycerine total amount meter, content of ashes is 4.1%.
Above-mentioned crude glycerine (A) 600g is added in the four-neck flask of 1000mL, at room temperature, is passed through hydrogen chloride gas
128g, gradually has the solid of fine particle to salt out in system；At 60 DEG C, the glycerol having led to hydrogen chloride gas is transferred to filter
Cloth aperture is to carry out on the filter press of 800 mesh filtering removing the slaine separating out, glycerol (C1) 706g after being processed（68.5%
Glycerol, 18.1% hydrogen chloride, 12.2% water, 0.06% sodium chloride, and the impurity of surplus.Wherein, based on glycerol total amount meter after processing,
Content of ashes is 0.23%）.
The preparation of epoxychloropropane
Glycerol (C1) after above-mentioned process is transferred in another 2000mL four-neck flask, adds 38.3g adipic acid（99%, W/
W）, heating content to temperature is to be passed through hydrogen chloride gas under stirring when 100 DEG C, is passed through hydrogen chloride gas 20h in 110 DEG C, altogether
It is passed through hydrogen chloride gas 387g, wherein by the water being formed, hydrogen chloride and dichlorohydrin vacation ternary azeotrope constantly from reactant
In system, removal obtains carry-over, and dichlorohydrin is steamed by vacuum distillation after terminating and obtains steaming thing by reaction.Reaction finishes, will
Carry-over and steaming thing are mixed to get dichlorohydrin mixed liquor 967g, and wherein dichloropropanol content is 54.8%, and yield is 78.2%
（Calculated with amounts of glycerol）.
Dichlorohydrin mixed liquor obtained above is transferred in 3000mL four-neck flask, heats content to 100 DEG C, to
Deca 30% sodium hydroxide solution 602g in system, after carrying out cyclization, is fractionated into post and obtains epoxychloropropane 286g, yield
For 75.4%（Calculated with dichlorohydrin amount）, the content of epoxychloropropane is 99.57%, moisture 0.06%, colourity 14（APHA）, close
Degree 1.181g/cm3.
Embodiment 2
The process of crude glycerine
The composition of raw material crude glycerine is with embodiment 1.
Above-mentioned crude glycerine (A) 600g is added in the four-neck flask of 1000mL, is -98.2KPa in gauge pressure, 75 DEG C of temperature
Under carry out vacuum distillation and remove moisture removal, obtain crude glycerine (B) 560g after eliminating water（86.3% glycerol, 8.2% water, 3.9% sodium chloride, remaining
Measure as impurity；Wherein, based on crude glycerine total amount meter after eliminating water, content of ashes is 4.2%）；It is passed through in crude glycerine (B) to after eliminating water
Hydrogen chloride gas 114g, gradually has the solid of fine particle to salt out in system；At 60 DEG C, the sweet of hydrogen chloride gas will be led to
Oil is transferred to carry out on the filter press that filter cloth aperture is 800 mesh filtering and removes the slaine separating out, glycerol (C2) after being processed
653g（74.0% glycerol, 17.5% hydrogen chloride, 7.0% water, 0.07% sodium chloride, balance of impurity；Wherein, based on glycerol after processing
Total amount meter, content of ashes is 0.32%）.
The preparation of epoxychloropropane
The preparation method of epoxychloropropane is with embodiment 1.
Obtain dichlorohydrin mixed liquor 946g, wherein dichloropropanol content 59.9% through chlorination, yield is 83.7%（With glycerol
Amount calculates）.
The above-mentioned dichlorohydrin mixed liquor that obtains is cyclized with 30% sodium hydroxide solution 645g, is obtained epoxychloropropane
322g, yield is 79.2%（Calculated with dichlorohydrin amount）, the content of epoxychloropropane is 99.25%, moisture 0.07%, colourity 10
（APHA）, density 1.182g/cm3.
Embodiment 3
The process of crude glycerine
The composition of raw material crude glycerine, inventory and processing method are with embodiment 2.
Difference is, crude glycerine (B) 538g after the eliminating water obtaining（89.8% glycerol, 4.5% water, 4% sodium chloride, surplus
For impurity；Wherein, based on crude glycerine total amount meter after eliminating water, content of ashes is 4.3%）, it is passed through 106g hydrogen chloride gas during desalination,
Glycerol (C2) 624g after being processed（77.5% glycerol, 17.1% hydrogen chloride, 3.9% water, 0.07% sodium chloride, balance of impurity；Its
In, based on glycerol total amount meter after processing, content of ashes is 0.3%）.
The preparation of epoxychloropropane
The preparation method of epoxychloropropane is with embodiment 1.
Obtain dichlorohydrin mixed liquor 943g, wherein dichloropropanol content 63.4% through chlorination, yield is 88.3%（With glycerol
Amount calculates）.
The above-mentioned dichlorohydrin mixed liquor that obtains is cyclized with 30% sodium hydroxide solution 680g, is obtained epoxychloropropane
359g, yield is 83.7%（Calculated with dichlorohydrin amount）, the content of epoxychloropropane is 99.40%, moisture 0.06%, colourity 8
（APHA）, density 1.182g/cm3.
Embodiment 4
The process of crude glycerine
The composition of raw material crude glycerine, inventory and processing method are with embodiment 2.
Difference is, crude glycerine (B) 520g after the eliminating water obtaining（93.0% glycerol, 1.1% water, 4.2% sodium chloride, remaining
Measure as impurity；Wherein, based on crude glycerine total amount meter after eliminating water, content of ashes is 4.4%）, it is passed through 99g hydrogen chloride gas during desalination,
Glycerol (C2) 598g after being processed（80.9% glycerol, 16.6% hydrogen chloride, 0.9% water, 0.08% sodium chloride, balance of impurity；Its
In, based on glycerol total amount meter after processing, content of ashes is 0.34%）.
The preparation of epoxychloropropane
The preparation method of epoxychloropropane is with embodiment 1.
Obtain dichlorohydrin mixed liquor 942g, wherein dichloropropanol content 66.6% through chlorination, yield is 92.6%（With glycerol
Amount calculates）.
The above-mentioned dichlorohydrin mixed liquor that obtains is cyclized with 30% sodium hydroxide solution 713g, is obtained epoxychloropropane
395g, yield is 87.8%（Calculated with dichlorohydrin amount）, the content of epoxychloropropane is 99.50%, moisture 0.07%, colourity 12
（APHA）, density 1.181g/cm3.
Embodiment 5
The process of crude glycerine
Raw material crude glycerine is consisting of the following：10.3% glycerol, 77.6% water, 11.4% sodium chloride, balance of impurity；Wherein, base
In crude glycerine total amount meter, content of ashes is 11.9%.
The inventory of crude glycerine and processing method are with embodiment 2.
Difference is, obtains crude glycerine (B) 136g after eliminating water（45.4% glycerol, 1.3% water, 50.23% sodium chloride, remaining
Measure as impurity；Wherein, based on crude glycerine total amount meter after eliminating water, content of ashes is 50.5%）, during desalination, it is passed through 15g hydrogen chloride gas
Body, glycerol (C2) 83.0g after being processed（74.5% glycerol, 18.3% hydrogen chloride, 2.1% water, 0.08% sodium chloride, balance of miscellaneous
Matter；Wherein, based on glycerol total amount meter after processing, content of ashes is 0.45%）.
The preparation of epoxychloropropane
The preparation method of epoxychloropropane is with embodiment 1.
Difference is, adds adipic acid 4.9g, is passed through hydrogen chloride gas 49g, obtains dichlorohydrin mixing through chlorination
Liquid 125g, wherein dichloropropanol content 62.1%, yield is 89.4%（Calculated with amounts of glycerol）.
The above-mentioned dichlorohydrin mixed liquor that obtains is cyclized with 30% sodium hydroxide solution 88g, is obtained epoxychloropropane
46g, yield is 82.5%（Calculated with dichlorohydrin amount）, the content of epoxychloropropane is 99.3%, moisture 0.05%, colourity 11
（APHA）, density 1.182g/cm3.
Embodiment 6
The process of crude glycerine
Raw material crude glycerine is consisting of the following：46.7% glycerol, 45.7% water, 6.8% sodium chloride, balance of impurity；Wherein, base
In crude glycerine total amount meter, content of ashes is 7.1%.
The inventory of crude glycerine and processing method are with embodiment 2.
Difference is, obtains crude glycerine (B) 331g after eliminating water（84.7% glycerol, 1.5% water, 12.3% sodium chloride, remaining
Measure as impurity；Wherein, based on crude glycerine total amount meter after eliminating water, content of ashes is 12.7%）, during desalination, it is passed through 59g hydrogen chloride gas
Body, glycerol (C2) 350g after being processed（80.2% glycerol, 17.0% hydrogen chloride, 1.4% water, 0.09% sodium chloride, balance of miscellaneous
Matter；Wherein, based on glycerol total amount meter after processing, content of ashes is 0.39%）.
The preparation of epoxychloropropane
The preparation method of epoxychloropropane is with embodiment 1.
Difference is, adds adipic acid 22.2g, is passed through hydrogen chloride gas 224g, obtains dichlorohydrin through chlorination and mixes
Close liquid 543g, wherein dichloropropanol content 65.6%, yield is 90.7%（Calculated with amounts of glycerol）.
The above-mentioned dichlorohydrin mixed liquor that obtains is cyclized with 30% sodium hydroxide solution 405g, is obtained epoxychloropropane
215g, yield is 84.3%（Calculated with dichlorohydrin amount）, the content of epoxychloropropane is 99.5%, moisture 0.07%, colourity 9
（APHA）, density 1.182g/cm3.
Embodiment 7
The process of crude glycerine
Raw material crude glycerine is consisting of the following：92.5% glycerol, 4.6% water, 1.7% sodium chloride, balance of impurity；Wherein, it is based on
Crude glycerine total amount meter, content of ashes is 2.1%.
The inventory of crude glycerine and processing method are with embodiment 2.
By dehydration, obtain crude glycerine (B) 579g after eliminating water（95.8% glycerol, 1.2% water, 1.8% sodium chloride, balance of miscellaneous
Matter；Wherein, based on crude glycerine total amount meter after eliminating water, content of ashes is 2.5%）, it is passed through 114g hydrogen chloride gas during desalination, obtain
Glycerol (C2) 683g after process（81.3% glycerol, 16.6% hydrogen chloride, 1.0% water, 0.05% sodium chloride, balance of impurity；Wherein,
Based on glycerol total amount meter after processing, content of ashes is 0.48%）.
The preparation of epoxychloropropane
The preparation method of epoxychloropropane is with embodiment 1.
Difference is, adds adipic acid 44g, is passed through hydrogen chloride gas 444g, obtains dichlorohydrin mixing through chlorination
Liquid 1082g, wherein dichloropropanol content 67.0%, yield is 93.2%（Calculated with amounts of glycerol）.
The above-mentioned dichlorohydrin mixed liquor that obtains is cyclized with 30% sodium hydroxide solution 824g, is obtained epoxychloropropane
459g, yield is 88.3%（Calculated with dichlorohydrin amount）, the content of epoxychloropropane is 99.6%, moisture 0.03%, colourity 7
（APHA）, density 1.182g/cm3.
Comparative example 1.
The untreated preparation being directly used in epoxychloropropane of crude glycerine.
The composition of raw material crude glycerine, inventory and epoxychloropropane preparation method are with embodiment 1.
Difference is, when being passed through chlorination hydrogen chloride, has a large amount of salt particles to separate out in system, impact chlorination reaction is just
Often carry out.It is passed through hydrogen chloride gas 484g, obtain dichlorohydrin mixed liquor 882g, wherein dichloropropanol content 50.0% through chlorination,
Yield is 65.2%（Calculated with amounts of glycerol）, the amount obtaining solid salt particles is 21g.
The above-mentioned dichlorohydrin mixed liquor that obtains is cyclized with 30% sodium hydroxide solution 502g, is obtained epoxychloropropane
213g, yield is 67.3%（Calculated with dichlorohydrin amount）, the content of epoxychloropropane is 99.53%, moisture 0.08%, colourity 11
（APHA）, density 1.182g/cm3.
Comparative example 2
Prepare epoxychloropropane with 99.5% smart glycerol.
The preparation method of epoxychloropropane is with embodiment 1.
Difference is, adds adipic acid 47.3g, is passed through hydrogen chloride gas 597g, obtains dichlorohydrin through chlorination and mixes
Close liquid 1020g, wherein dichloropropanol content 76.2%, yield is 92.9%（Calculated with amounts of glycerol）.
The above-mentioned dichlorohydrin mixed liquor that obtains is cyclized with 30% sodium hydroxide solution 883g, is obtained epoxychloropropane
480g, yield is 86.3%（Calculated with dichlorohydrin amount）, the content of epoxychloropropane is 99.49%, moisture 0.06%, colourity 9
（APHA）, density 1.181g/cm3.
By above example and comparative example, when untreated crude glycerine is directly used in chlorination, have a large amount of nothings
Machine salts out, and easily causes line clogging aborning, and impact reaction is normally carried out；The moisture containing in glycerol after process is got over
Many, chlorination efficiency is lower, and epoxychloropropane yield is lower；The crude glycerine of different content glycerol after processing the process obtaining
Chlorination efficiency and epoxychloropropane yield are suitable with 99.5% smart glycerol.
Industrial applicability
As described above, the processing method of crude glycerine of the present invention, and using glycerol production epoxychloropropane after processing
Method in industry and industrial there is utilizability and practicality.
Claims (13)
1. a kind of crude glycerine processing method is it is characterised in that the method comprises the steps：
A crude glycerine is contacted by () with hydrogen chloride gas, separate out insoluble solid；
B () removes the described solid separating out, glycerol after being processed by solid-liquid separation.
2. a kind of crude glycerine processing method is it is characterised in that the method comprises the steps：
A crude glycerine is removed at least a portion water by (), obtain crude glycerine after eliminating water；
B crude glycerine after described eliminating water is contacted by () with hydrogen chloride gas, separate out insoluble solid；
C () removes the described solid separating out, glycerol after being processed by solid-liquid separation.
3. crude glycerine processing method according to claim 1 and 2, the wherein crude glycerine in step (a) comprises 5 weight % extremely
The glycerol of 95 weight %, the water of 1 weight % to 80 weight %, and 1 weight % is to the slaine of 30 weight %.
4. crude glycerine processing method according to claim 1, comprises in glycerol after the described process that wherein step (b) obtains
The glycerol of 5 weight % to 90 weight %, the hydrogen chloride of 5 weight % to 40 weight %, the water of 0.5 weight % to 60 weight %, and
Slaine less than 1 weight %.
5. crude glycerine processing method according to claim 2, wraps in crude glycerine after the described eliminating water that wherein step (a) obtains
Glycerol containing 30 weight % to 99 weight %, the water of 0.1 weight % to 10 weight %, and 1 weight % is to the metal of 55 weight %
Salt.
6. crude glycerine processing method according to claim 1 and 2, when being wherein passed through hydrogen chloride gas, the gauge pressure of system is-
0.1MPa to 1MPa, the described amount being passed through hydrogen chloride is the 5% to 70% of crude glycerine weight, described contacts with hydrogen chloride gas
After crude glycerine or eliminating water, the initial temperature of crude glycerine is 20 DEG C to 200 DEG C, crude glycerine after crude glycerine or eliminating water in solid-liquid separation
Temperature is 20 DEG C to 200 DEG C.
7. crude glycerine processing method according to claim 2, comprises in glycerol after the described process that wherein step (c) obtains
The glycerol of 50 weight % to 95 weight %, the hydrogen chloride of 1 weight % to 30 weight %, the water of 0.1 weight % to 20 weight %, and
Slaine less than 1 weight %.
8. a kind of preparation method of epoxychloropropane is it is characterised in that the method comprises the steps：
(a) processed using the method described in any one of claim 1-7 after glycerol；
(b) in the presence of carboxylic acidss catalyst, glycerol or its mixture and hydrogen chloride after the described process that step (a) is obtained
Gas reaction, prepares dichlorohydrin；
C dichlorohydrin and cyclizing agent are carried out removing hcl reaction by (), prepare epoxychloropropane.
9. the preparation method of epoxychloropropane according to claim 8 is it is characterised in that described carboxylic acidss catalyst is vinegar
The combination of one or more of acid, malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, Azelaic Acid and decanedioic acid；And/or, described
The consumption of carboxylic acidss catalyst be process after glycerol mole 0.1% to 10%；And/or, the reaction temperature of step (b) is 80
DEG C to 130 DEG C；And/or, the response time of step (b) is 1h to 20h；And/or, glycerol and hydrogen chloride after processing in step (b)
Mol ratio be 1:2 to 1:5.
10. the preparation method of epoxychloropropane according to claim 9 is it is characterised in that described carboxylic acidss catalyst
Consumption be process after glycerol mole 1% to 6%；And/or, the reaction temperature of step (b) is 100 DEG C to 120 DEG C；And/or,
The response time of step (b) is 5h to 15h；And/or, after processing in step (b), glycerol and the mol ratio of hydrogen chloride are 1:2 to 1:
3.
A kind of 11. glycerin compositions, wherein contain the glycerol comprising 5 weight % to 90 weight %, 5 weight % are to 40 weight %
Hydrogen chloride, the water of 0.5 weight % to 60 weight %, and the slaine less than 1 weight %.
12. glycerin compositions according to claim 11 are it is characterised in that described glycerin compositions comprise 50 weight % extremely
The glycerol of 90 weight %, the hydrogen chloride of 5 weight % to 30 weight %, the water of 1 weight % to 20 weight %, more than 0.02 weight %
Slaine less than 1 weight %.
A kind of 13. methods preparing epoxide and its derivant, wherein, using described in claim 11 or claim 12
Glycerin compositions be prepared as initiation material.
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| CN113234041B (en) * | 2021-04-07 | 2023-03-10 | 江苏瑞恒新材料科技有限公司 | Preparation method of epichlorohydrin |
| CN113999190A (en) * | 2021-11-19 | 2022-02-01 | 江苏瑞祥化工有限公司 | Method for decoloring microchannel continuous flow epichlorohydrin and hydrogen peroxide |
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| WO2006020234A1 (en) * | 2004-07-21 | 2006-02-23 | Dow Global Technologies Inc. | Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin |
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