CN105368090B - Reduce the preparation method of the caramel colorant of 4 methylimidazole contents - Google Patents
Reduce the preparation method of the caramel colorant of 4 methylimidazole contents Download PDFInfo
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- CN105368090B CN105368090B CN201510812769.8A CN201510812769A CN105368090B CN 105368090 B CN105368090 B CN 105368090B CN 201510812769 A CN201510812769 A CN 201510812769A CN 105368090 B CN105368090 B CN 105368090B
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- caramel colorant
- amino acid
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- sugar
- glucose
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- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 235000013736 caramel Nutrition 0.000 title claims abstract description 65
- 239000003086 colorant Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XDKUKGIJDNUFGK-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CN=C[N]1 XDKUKGIJDNUFGK-UHFFFAOYSA-N 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 150000001413 amino acids Chemical class 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 235000011389 fruit/vegetable juice Nutrition 0.000 claims abstract description 8
- 238000009413 insulation Methods 0.000 claims abstract description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 74
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 32
- 239000008103 glucose Substances 0.000 claims description 28
- 239000004471 Glycine Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 235000001014 amino acid Nutrition 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 11
- GUBGYTABKSRVRQ-PICCSMPSSA-N D-Maltose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000004472 Lysine Substances 0.000 claims description 6
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 6
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 5
- 235000004279 alanine Nutrition 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 235000013379 molasses Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000006188 syrup Substances 0.000 claims description 3
- 235000020357 syrup Nutrition 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 238000005516 engineering process Methods 0.000 abstract description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical class CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000796 flavoring agent Substances 0.000 description 6
- 235000019634 flavors Nutrition 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 235000018977 lysine Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920002527 Glycogen Polymers 0.000 description 4
- 235000018417 cysteine Nutrition 0.000 description 4
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 4
- 229940096919 glycogen Drugs 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000013056 hazardous product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002552 multiple reaction monitoring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000019640 taste Nutrition 0.000 description 2
- 231100000027 toxicology Toxicity 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RRUYWEMUWIRRNB-LURJTMIESA-N (2s)-6-amino-2-[carboxy(methyl)amino]hexanoic acid Chemical compound OC(=O)N(C)[C@H](C(O)=O)CCCCN RRUYWEMUWIRRNB-LURJTMIESA-N 0.000 description 1
- VGBASMXDKFZLAK-MIOZVUHLSA-N 1,2,2,3,4-pentadeuterio-4-methylimidazolidine Chemical compound CC1(N(C(N(C1)[2H])([2H])[2H])[2H])[2H] VGBASMXDKFZLAK-MIOZVUHLSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 206010010904 Convulsion Diseases 0.000 description 1
- 241001337814 Erysiphe glycines Species 0.000 description 1
- 239000000940 FEMA 2235 Substances 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010811 Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- 201000011510 cancer Diseases 0.000 description 1
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- 230000036461 convulsion Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
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- 230000036252 glycation Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
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- -1 nitrogen-containing heterocycle compound Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
The invention discloses a kind of preparation method of the caramel colorant for reducing by 4 methylimidazole contents, comprise the following steps：Raw material sugar water is first configured to sugar juice, is subsequently adding and is stirred as the ammoniacal liquor and addition amino acid of catalyst, be then rapidly heated to 140 ± 2 DEG C of 55~65min of insulation reaction；The product of gained is cooled to rapidly≤50 DEG C, by the product concentration after cooling, caramel colorant liquid after must concentrating；Caramel colorant liquid after concentration is further dried to moisture content≤5%, the caramel colorant of solid-state is obtained.The level of the present invention 4 methylimidazoles in production link significantly reduces caramel colorant by adding the method for amino acid, so that the edible caramel colorant of the high-quality and safety for realizing producing low 4 methylimidazole content on the basis of existing production technology and facility is not changed.
Description
Technical field
The invention provides a kind of method for controlling its 4-methylimidazole to be formed in caramel colorant production process, belong to food
The technical field that product safe manufacturing flow is reconstructed and its hazardous material is controlled.
Background technology
Caramel colorant is a kind of Applications in Food Industry toning, seasoning, the adding ingredient in perfume widely.It is with
Glucose, maltose, sucrose, starch syrup, wood molasses etc. are raw material, using ammonium sulfite, ammonia process, sulphite process, general
Liquid or mealy pigment that logical method etc. is made, are one of additives of yield maximum in China's natural pigment, are widely used in adjusting
In many based foods such as taste product, soda, brewed wine, bakery, candy, to increase organoleptic quality, commodity value is improved.20
The sixties in century, caramel colorant is once because containing 4-methylimidazole, by some country's disablings, thus its safety issue also draws
Send out extensive concern worldwide.4-methylimidazole is a kind of nitrogen-containing heterocycle compound, beautiful with strong cause convulsion effect
Country's Toxicology Program of state (NTP) is tested by animal toxicology proves that 4-methylimidazole has carcinogenicity, international cancer mechanism
(IARC) 2B groups " the possible carcinogenic substance of the mankind " are classified as.California, USA Environmental Health risk assessment office
(OEHHA) the human body daily intaking amount of suggestion 4-methylimidazole is not to be exceeded 29 μ g.4-methylimidazole is mainly derived from ammonia process and Asia
The caramel colorant of ammonium sulfate method production, at present studies have reported that by controlling reaction condition, such as being reacted to subtract stage by stage
The generation of few 4-methylimidazole, or use physical method such as ultrafiltration etc. to process caramel colorant product to remove 4- methyl miaows
Azoles.But the production technology of caramel colorant is complex, and reaction condition is difficult to control to, and the operation of physics removal method is comparatively laborious,
Causing production cost increases, it is difficult to be promoted.At present, 4- methyl in the caramel colorant that traditional ammonia process and ammonium sulfite are produced
Imidazole content nearly all exceedes national standard, and (GB8817-2001 specifies that 4-methylimidazole content is not in ammonium (ammonia) method caramel colorant
Can exceed that 200ppm).Therefore, caramel colorant industry urgently a kind of simple and easy to apply, cost is controllable, excellent effect manufacturing technology with
Realize the large-scale production of the high-quality and safety caramel colorant of low 4-methylimidazole content.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation side of the caramel colorant for reducing 4-methylimidazole content
Method；The level of present invention 4-methylimidazole in production link significantly reduces caramel colorant by adding the method for amino acid,
So as to realize the food of the high-quality and safety that low 4-methylimidazole content is produced on the basis of existing production technology and facility is not changed
Use caramel colorant.
In order to solve the above-mentioned technical problem, the present invention provides a kind of preparation of the caramel colorant for reducing 4-methylimidazole content
Method, comprises the following steps：
1) it is 45~55g/100mL's (preferably 50g/100mL, 50% (w/v)) that raw material sugar water, is configured into concentration
Sugar juice；
Added in sugar juice and form reaction system, the NH of the ammoniacal liquor as the ammoniacal liquor of catalyst4 +With the original in sugar juice
The mass ratio for expecting sugar is 6%；
2), in step 1) obtained by reaction system in add amino acid stir；The amino acid and step 1) in
The mass ratio of raw material sugar for 1.5~12% (preferably 3~9%, more preferably 5~7%)；
3), by step 2) obtained by reaction solution be rapidly heated (that is, control heating rate be 3~4 DEG C/min) to 140 ± 2
DEG C, 55~65min of insulation reaction (preferably 60min)；
4), by step 3) obtained by product (be liquid) be cooled to≤50 DEG C (completing to lower the temperature in 5min) rapidly,
By the product concentration after cooling, caramel colorant liquid after must concentrating；
5), caramel colorant liquid (caramel colorant of liquid) after concentration is further dried to moisture content≤5% (quality %)
Afterwards, the caramel colorant of solid-state (powder or particle) is obtained.
As the improvement of the preparation method of the caramel colorant of reduction 4-methylimidazole content of the invention：
The step 4) in, the product after cooling is concentrated into 33~38 ° of B é, caramel colorant liquid after must concentrating.
As the further improvement of the preparation method of the caramel colorant of reduction 4-methylimidazole content of the invention：The ammonia
Base acid is edible grade amino acid, and the edible grade amino acid is glycine, alanine, lysine or cysteine.
As the further improvement of the preparation method of the caramel colorant of reduction 4-methylimidazole content of the invention：The original
Material sugar is glucose, maltose, sucrose, starch syrup or wood molasses.
As the further improvement of the preparation method of the caramel colorant of reduction 4-methylimidazole content of the invention：The ammonia
Base acid is glycine, and the raw material sugar is glucose；The additive capacity of the glycine is the 5~7% of glucose quality.
As the further improvement of the preparation method of the caramel colorant of reduction 4-methylimidazole content of the invention：The step
Rapid drying 5) is：Normal pressure or low pressure are dried, freeze-drying.
Remarks explanation：Actual industrial metaplasia preferred belt vacuum drying or microwave-hot air drying when producing.
As the further improvement of the preparation method of the caramel colorant of reduction 4-methylimidazole content of the invention：The step
It is rapid 1) in ammoniacal liquor refer to the aqueous solution containing ammonia 25%~28% (quality %).
In caramel colorant production process, on the one hand the complicated chemical reaction for occurring can promote a large amount of new chemicals
Matter is generated, and assigns the distinctive local flavor of caramel colorant and color and luster, while can also produce some chemical hazard things, brings potential safety hazard.
In actual applications, 4-methylimidazole has become caramel colorant and its characteristic hazardous material index of extension product is controlled
System.The present invention uses and the method for amino acid is added in dispensing to control heat on the basis of existing caramel colorant production technology
The generation of 4-methylimidazole in course of reaction.By screening amino acid classes and optimizing its addition, obtain 4-methylimidazole and contain
The amount high-quality caramel colorant product that low, color and luster is scarlet, color rate is high；The present invention is easy to operate, and fringe cost is low, without newly added equipment
With change technological parameter, in the food industry with extensive application value.
Compared with prior art, the present invention has advantages below：
(1) while 4-methylimidazole content in significantly reducing product, the Red Index or color rate of product can be improved,
And the original local flavor of caramel colorant is not influenceed, greatly lift its edible safety and product quality；
(2) easy to operate, fringe cost is low, easy to spread in food service industry without newly added equipment and change technological parameter.
In sum, the method for the present invention with the addition of a certain amount of in the blending process of traditional ammonia process production caramel colorant
Amino acid, significantly suppress the formation of 4-methylimidazole in carbonyl ammonia condensation reaction, and not influence the original wind of caramel colorant
Taste and quality, greatly lift its edible safety.
Specific embodiment
The present invention is expanded on further with reference to specific embodiment.
Comparative example 1 (taking glucose as the comparative example of glycogen material),
Glucose and water are mixed, the glucose solution (abbreviation liquid glucose) that concentration is 50% (w/v), above-mentioned liquid glucose is prepared into
Reactor is transferred to, by liquid glucose quality 6% (with NH4 +Amount and liquid glucose dry quality meter) ratio add ammoniacal liquor (contain ammonia
The aqueous solution of 25%~28% (quality %)) as catalyst, stir.Reaction solution is rapidly heated, and (that is, control heats up
Speed is 3~4 DEG C/min) to 140 DEG C, control temperature reacts 60min at 140 ± 2 DEG C, after reaction terminates, lower the temperature rapidly (
Cooling is completed in 5min) to less than 50 DEG C, by above-mentioned reaction solution vacuum concentration (in 40 DEG C) to viscous liquid (33~38 ° of B
é), freeze-drying, obtains solid caramel pigment powder (water content is 3% or so, similarly hereinafter).It is as with glucose using this product
The blank sample of glycogen material.
Remarks explanation：
50% (w/v) glucose solution, i.e. glucose containing 50g in 100mL glucose solutions.Following case is similar.
By liquid glucose quality 6% (with NH4 +Amount and liquid glucose dry quality meter) ratio add ammoniacal liquor, i.e. ammoniacal liquor
NH4 +It is 6% with the mass ratio of the glucose in sugar juice.Following case is similar.
Embodiment 1,
Glucose and water are mixed, the glucose solution that concentration is 50% (w/v) is prepared into, above-mentioned liquid glucose is transferred to reaction
Kettle, by liquid glucose quality 6% (with NH4 +Amount and liquid glucose dry quality meter) ratio add ammoniacal liquor (contain ammonia 25%~28%
The aqueous solution of (quality %), following case is equivalent) as catalyst, while pressing liquid glucose 6% (with the quality and liquid glucose of glycine
The quality meter of dry) ratio add glycine, fully dissolving, stir.Reaction solution is rapidly heated and (that is, is controlled
Heating rate is 3~4 DEG C/min) to 140 DEG C, 140 ± 2 DEG C of reaction 60min of control temperature, after reaction terminates, rapid cooling
Be concentrated in vacuo (at 40 DEG C) above-mentioned reaction solution to viscous liquid (33 to less than 50 DEG C by (cooling is completed in 5min)
~38 ° of B é, similarly hereinafter), freeze-drying obtains solid caramel pigment powder.
Remarks explanation：Sweet ammonia is added by the ratio of liquid glucose 6% (in terms of the quality of the quality of glycine and liquid glucose dry)
Acid, i.e. glycine is 6% with the mass ratio of glucose.Following case is similar.
Embodiment 2
Glucose and water are mixed, the glucose solution that concentration is 50% (w/v) is prepared into, above-mentioned liquid glucose is transferred to reaction
Kettle, by liquid glucose quality 6% (with NH4 +Amount and liquid glucose dry quality meter) ratio add ammoniacal liquor as catalyst, while
Lysine, fully dissolving are added by the ratio of liquid glucose 3% (in terms of the quality of the quality of lysine and liquid glucose dry), stirring is equal
It is even.Reaction solution is rapidly heated to 140 DEG C, 140 ± 2 DEG C of reaction 60min of control temperature after reaction terminates, are cooled to rapidly
Less than 50 DEG C, above-mentioned reaction solution is concentrated in vacuo to viscous liquid (at 40 DEG C), freeze-drying obtains solid caramel pigment
Powder.
Embodiment 3
Glucose and water are mixed, the glucose solution that concentration is 50% (w/v) is prepared into, above-mentioned liquid glucose is transferred to reaction
Kettle, by liquid glucose quality 6% (with NH4 +Amount and liquid glucose dry quality meter) ratio add ammoniacal liquor as catalyst, while
Alanine is added by the ratio of liquid glucose quality 6% (in terms of the quality of the quality of alanine and liquid glucose dry), fully dissolving is stirred
Mix uniform, reaction solution is rapidly heated to 140 DEG C, 140 ± 2 DEG C of reaction 60min of control temperature, after reaction terminates, rapid drop
Be concentrated in vacuo above-mentioned reaction solution to viscous liquid (at 40 DEG C) to less than 50 DEG C by temperature, and freeze-drying obtains solid caramel
Pink colour element end.
Embodiment 4
Glucose and water are mixed, the glucose solution that concentration is 50% (w/v) is prepared into, above-mentioned liquid glucose is transferred to reaction
Kettle, by liquid glucose quality 6% (with NH4 +Amount and liquid glucose dry quality meter) ratio add ammoniacal liquor as catalyst, while
Cysteine, fully dissolving are added by liquid glucose quality 9% (in terms of the quality of the quality of cysteine and liquid glucose dry) ratio,
Stir, reaction solution is rapidly heated to 140 DEG C, 140 ± 2 DEG C of reaction 60min of control temperature, after reaction terminates, rapidly
Less than 50 DEG C are cooled to, above-mentioned reaction solution is concentrated in vacuo to viscous liquid (at 40 DEG C), freeze-drying obtains solid burnt
Fried sugar element powder.
Comparative example 2 (taking maltose as the comparative example of glycogen material)
Maltose and water are mixed, the maltose solution that concentration is 50% (w/v) is prepared into, above-mentioned liquid glucose is transferred to reaction
Kettle, by liquid glucose quality 6% (with NH4 +Amount and liquid glucose dry quality meter) ratio add ammoniacal liquor as catalyst, stirring
Uniformly.Reaction solution is rapidly heated to 140 DEG C, control temperature reacts 60min at 140 ± 2 DEG C, after reaction terminates, rapid drop
Be concentrated in vacuo above-mentioned reaction solution to viscous liquid (at 40 DEG C) to less than 50 DEG C by temperature, and freeze-drying obtains solid caramel
Pigment powder.Using this product as the blank sample with maltose as glycogen material.
Embodiment 5
Maltose and water are mixed, the maltose solution that concentration is 50% (w/v) is prepared into, above-mentioned liquid glucose is transferred to reaction
Kettle, by liquid glucose quality 6% (with NH4 +Amount and liquid glucose dry quality meter) ratio add ammoniacal liquor as catalyst, while
Glycine is added by the ratio of liquid glucose quality 9% (in terms of the quality of the quality of glycine and liquid glucose dry), fully dissolving is stirred
Mix uniform, reaction solution is rapidly heated to 140 DEG C, 140 ± 2 DEG C of reaction 60min of control temperature, after reaction terminates, rapid drop
Be concentrated in vacuo above-mentioned reaction solution to viscous liquid (at 40 DEG C) to less than 50 DEG C by temperature, and freeze-drying obtains solid caramel
Pink colour element end.
Comparative example 3-1
Glucose and water are mixed, the glucose solution that concentration is 50% (w/v) is prepared into, above-mentioned liquid glucose is transferred to reaction
Kettle, by liquid glucose quality 6% (with NH4 +Amount and liquid glucose dry quality meter) ratio add ammoniacal liquor as catalyst, while
Glycine, fully dissolving are added by the ratio of liquid glucose 1% (in terms of the quality of the quality of glycine and liquid glucose dry), stirring is equal
It is even.Reaction solution is rapidly heated to 140 DEG C, 140 ± 2 DEG C of reaction 60min of control temperature after reaction terminates, are cooled to rapidly
Less than 50 DEG C, above-mentioned reaction solution is concentrated in vacuo to viscous liquid (at 40 DEG C), freeze-drying obtains solid caramel pigment
Powder.
Comparative example 3-2
Glucose and water are mixed, the glucose solution that concentration is 50% (w/v) is prepared into, above-mentioned liquid glucose is transferred to reaction
Kettle, by liquid glucose quality 6% (with NH4 +Amount and liquid glucose dry quality meter) ratio add ammoniacal liquor as catalyst, while
Glycine, fully dissolving, stirring are added by the ratio of liquid glucose 15% (in terms of the quality of the quality of glycine and liquid glucose dry)
Uniformly.Reaction solution is rapidly heated to 140 DEG C, 140 ± 2 DEG C of reaction 60min of control temperature, after reaction terminates, rapid cooling
To less than 50 DEG C, above-mentioned reaction solution is concentrated in vacuo to viscous liquid (at 40 DEG C), freeze-drying obtains solid caramel color
Plain powder.
Experiment 1, the 4-methylimidazole content of caramel colorant, color rate and Red Index assay method
(1) measure of 4-methylimidazole content
Using UPLC-MS/MS methods, 4-methylimidazole-d5Isotopic standard product carry out 4-methylimidazole content for internal standard
Determine.Chromatographic condition：Chromatographic column：Varian Polaris RP (3 μm, 4.6mm × 100mm)；Mobile phase：A phases (contain for water
15mmol/L ammonium hydrogen carbonate), B phases are acetonitrile (ammonium hydrogen carbonate containing 15mmol/L)；Gradient elution：0-3min, 98%A；10-
13min, 60%A；15-25min, 98%A；Flow velocity：400 μ L/min, column temperature：35℃；Sample size：10μL.Mass Spectrometry Conditions：Ionization
Source is electron spray positive ion mode (ESI+), multiple-reaction monitoring (MRM)；Characteristic ion：The parent ion of 4-methylimidazole is 83.0,
Quantitative daughter ion 56.0, qualitative daughter ion 42.0；4-methylimidazole-d5The parent ion of Isotopic Internal Standard is 88.0, daughter ion
60.0。
(2) measure of color rate
It is accurate to weigh caramel colorant 1.000g (in terms of solid content), distilled water 10mL is added, stir molten with glass bar
Solution.Then move into 100mL volumetric flasks, washing lotion pours into volumetric flask, finally uses distilled water constant volume with distillation water washing beaker repeatedly
To 100mL, as 1% sample diluting liquid.The sample diluting liquid for drawing 10mL l% again enters 100mL volumetric flasks, plus distilled water
To scale, 0.1 ‰ sample diluting liquid is after shaking up.Because requiring its clear, so must be centrifuged through 2400r/min again
(or being filtered with filter paper).0.1 ‰ processed samples are poured into the cuvette of lcm, with spectrophotometer, is surveyed at 610nm
Fixed its absorbance A610Value, is repeatedly measured for several times, takes its average A610Value, is calculated as follows EBC colourities：Color rate (EBC units)=
A610×20000/0.076
(3) measure of Red Index
On the basis of (2) operate, wavelength is adjusted at 510nm, after readjusting zero point, measures its absorbance for A510
Value, is calculated as follows Red Index：Red Index=10 × lg (A510/A610)
The technical indicator of caramel colorant prepared by table 1, each case
Can be seen that amino acid by above-mentioned case has good inhibiting effect to the 4-methylimidazole in caramel colorant.
While reducing 4-methylimidazole content, embodiment 1 (addition glycine) color rate is significantly improved, Red Index reduction, but change
Less；Embodiment 3 (addition alanine) Red Index slightly has raising, but the reduction of color rate；Embodiment 4 (addition cysteine) is red
Index is improved, but color rate is significantly reduced；Embodiment 2 (addition lysine) has preferable inhibition to 4-methylimidazole, but grinds
Study carefully proof, lysine and reduced sugar occur Maillard reaction can generate a kind of most representational Advanced glycation endproducts-
, there is potentially hazardous property to human health in carboxymethyl-lysine.In terms of local flavor, embodiment 1,2,3 and comparative example 1, implement
Example 5 is not significantly different from comparative example 2, is respectively provided with the flavor characteristic of the distinctive slightly bitter taste of caramel colorant and burnt gas, but implement
Example 4 generates obvious excitant bad smell, has had a strong impact on the original local flavor of caramel colorant.Comparative example 3-1 is to 4- methyl
The inhibition of imidazoles is very small, although comparative example 3-2 maximum to the inhibition of 4-methylimidazole, the drop of Red Index
Width is also maximum, have impact on caramel colorant characteristic in itself.To sum up, in actual production, can be according to specifically to product property
Ask to select amino acid as additive, of the invention through Comprehensive Experiment, first-selected glycine, the addition of optimization is raw material saccharic amount
5-7%, the content of 4-methylimidazole in can significantly reducing product in this dosage range, improve color rate, and do not influence Jiao
The local flavor of fried sugar element, and glycine price is relatively low, and the influence to production cost is little.
Finally, in addition it is also necessary to it is noted that listed above is only several specific embodiments of the invention.Obviously, this hair
It is bright to be not limited to above example, there can also be many deformations.One of ordinary skill in the art can be from present disclosure
The all deformations directly derived or associate, are considered as protection scope of the present invention.
Claims (6)
1. 4-methylimidazole content can be reduced and the preparation method of the caramel colorant of original quality can be kept, it is characterized in that bag
Include following steps：
1) raw material sugar water, is configured to the sugar juice that concentration is 45~55g/100mL；
Added in sugar juice and form reaction system, the NH of the ammoniacal liquor as the ammoniacal liquor of catalyst4 +With the raw material sugar in sugar juice
Mass ratio be 6%；
2), in step 1) obtained by reaction system in add amino acid stir；The amino acid and step 1) in raw material
The mass ratio of sugar is 1.5~12%；
The amino acid is edible grade amino acid, and the edible grade amino acid is glycine, alanine, lysine or half Guang ammonia
Acid；
3), by step 2) obtained by reaction solution be rapidly heated to 140 ± 2 DEG C, 55~65min of insulation reaction；
4), by step 3) obtained by product be cooled to≤50 DEG C rapidly, by after cooling product concentration, after must concentrating
Caramel colorant liquid；
5), caramel colorant liquid after concentration is further dried to moisture content≤5%, the caramel colorant of solid-state is obtained.
2. the preparation method of caramel colorant according to claim 1, it is characterized in that：The step 4) in, after cooling
Product is concentrated into 33~38 ° of B é, caramel colorant liquid after must concentrating.
3. the preparation method of caramel colorant according to claim 2, it is characterized in that：The raw material sugar is glucose, malt
Sugar, sucrose, starch syrup or wood molasses.
4. the preparation method of caramel colorant according to claim 3, it is characterized in that：The amino acid is glycine, described
Raw material sugar is glucose；The additive capacity of the glycine is the 5~7% of glucose quality.
5. according to the preparation method of any described caramel colorant of Claims 1 to 4, it is characterized in that：The step 5) drying
For：Normal pressure or low pressure are dried, freeze-drying.
6. the preparation method of caramel colorant according to claim 1, it is characterized in that：The step 1) in ammoniacal liquor refer to containing ammonia
25%~28% aqueous solution.
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| CN107652707A (en) * | 2017-08-31 | 2018-02-02 | 广西顶俏食品有限公司 | The preparation technology of caramel colorant |
| CN108559303A (en) * | 2018-04-24 | 2018-09-21 | 肇庆焕发生物科技有限公司 | A kind of method of tetramethyl imidazoles in reduction caramel colorant |
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