CN114716843A - Ammonium sulfite method caramel color production process and caramel color - Google Patents
Ammonium sulfite method caramel color production process and caramel color Download PDFInfo
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- CN114716843A CN114716843A CN202210545367.6A CN202210545367A CN114716843A CN 114716843 A CN114716843 A CN 114716843A CN 202210545367 A CN202210545367 A CN 202210545367A CN 114716843 A CN114716843 A CN 114716843A
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- 239000000940 FEMA 2235 Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 49
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 62
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 21
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 235000020357 syrup Nutrition 0.000 claims description 18
- 239000006188 syrup Substances 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 150000003868 ammonium compounds Chemical class 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 238000004040 coloring Methods 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 4
- 150000001408 amides Chemical class 0.000 abstract description 4
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 7
- 235000013736 caramel Nutrition 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
- -1 ammonia compound Chemical class 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 235000020429 malt syrup Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 235000015277 pork Nutrition 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 244000299461 Theobroma cacao Species 0.000 description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000015784 hyperosmotic salinity response Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 235000015067 sauces Nutrition 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 235000013555 soy sauce Nutrition 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 244000088415 Raphanus sativus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000012706 ammonia caramel Nutrition 0.000 description 1
- 239000004125 ammonia caramel Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 235000012730 carminic acid Nutrition 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 235000020186 condensed milk Nutrition 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005837 enolization reaction Methods 0.000 description 1
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 description 1
- 235000012732 erythrosine Nutrition 0.000 description 1
- 239000004174 erythrosine Substances 0.000 description 1
- 229940011411 erythrosine Drugs 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940057059 monascus purpureus Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 229960001173 oxybenzone Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 1
- 229940075931 sodium dithionate Drugs 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000001040 synthetic pigment Substances 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
The invention discloses an ammonium sulfite method caramel color production process and caramel color, wherein sulfamic acid, aluminum isopropoxide and glycol are added into an ammonium sulfite method reaction system, the reaction system is controlled to be alkaline in the reaction process, and the reaction system is controlled to be acidic after the reaction is terminated; specifically, the pH value of the reaction system is controlled to be 7.0-7.5 in the reaction process; after the reaction is stopped, the pH value of the system is controlled to be 5.5-6.0. According to the invention, sulfamic acid, aluminum isopropoxide and ethylene glycol are added in the existing ammonium sulfite-method caramel color reaction system, and the sulfamic acid generates a large amount of substances containing amide and sulfonic acid groups in the reaction system, so that the polarity of the caramel color is enhanced, and the coloring effect of the caramel color is greatly improved; the aluminum isopropoxide and the ethylene glycol can improve the coloring stability and durability of the caramel color; therefore, the caramel color coloring effect prepared by the ammonium sulfite method caramel color production process is obviously improved.
Description
Technical Field
The invention relates to the technical field of caramel color production, in particular to an ammonium sulfite method caramel color production process and caramel color.
Background
Caramel color has a wide use tradition in China, is an edible pigment with the largest use amount, and has an extremely important role in the field of food. Caramel colors can be divided into four main categories according to different production processes: common caramel color, caustic sulfite caramel color, ammonia caramel color, ammonium sulfite caramel color. The caramel color produced by the ammonium sulfite method is prepared by taking carbohydrate as a main raw material and adding or not adding acid (alkali) in the presence of an ammonia compound and sulfite.
The ammonium sulfite caramel has negative charges, has good acid resistance and salt resistance, has relatively strong coloring capability and is widely applied to the food industry. GB 2760 supplement 2014 stipulate the national food safety standard food additive use standard: the ammonium sulfite caramel color can be used in the production and processing of condensed milk, various beverages, cocoa products, chocolate products, candies, paste, instant grains, biscuits, soy sauce and sauce products. In China, the caramel color of the ammonium sulfite method is one of main ingredients of soy sauce and sauce products. The ammonium sulfite method has wide application range of caramel color and high cost performance, is favored by vast food factories, and the output and sales amount of the ammonium sulfite method accounts for more than 60 percent of the total amount of the caramel color product.
But relative to other pigments such as natural pigment red yeast, sorghum red and radish red; compared with synthetic pigments such as erythrosine, sunset yellow, lemon yellow, carmine and the like, the ammonium sulfite method has the advantages of weak caramel color tinting strength, slow coloring, relatively narrow coloring range and relatively poor coloring stability. The invention aims to obviously improve the coloring strength, speed, applicable range and stability of the ammonium sulfite-method caramel color through a process technology for improving the coloring power of the ammonium sulfite-method caramel color so as to meet the market requirements and promote the healthy development of the caramel color industry.
Disclosure of Invention
The invention aims to provide a production process of caramel color by an ammonium sulfite method, which solves the problem of poor coloring effect of prepared caramel color caused by the existing production technology of the caramel color by the ammonium sulfite method.
In addition, the invention also provides the caramel color prepared by the ammonium sulfite method caramel color production process.
The invention is realized by the following technical scheme:
a process for preparing caramel color by ammonium sulfite method includes adding sulfamic acid, aluminium isopropoxide and glycol to the reaction system of ammonium sulfite method, controlling the reaction system to be alkaline in reaction process and controlling the reaction system to be acidic after reaction is finished.
In the reaction system of the prior art for producing caramel color by an ammonium sulfite method, sulfite, ammonia or ammonium compounds are added into raw syrup for Maillard reaction.
The syrup and the free amino groups in ammonia or ammonium compounds undergo a series of reactions including condensation, dehydrogenation, rearrangement, isomerization and the like to finally form brown polymers or copolymers containing nitrogen, which are called melanoids, and the melanoids are complex high-molecular mixtures with unknown molecular structures, and contain unsaturated bonds, heterocyclic structures and some residues.
In the reaction process, the product of the Maillard reaction can interact with sulfite ions to generate an oxidation reaction to generate a dark-color high molecular compound, so that the tinting strength of the product is improved, the degree of the oxidation reaction is related to the content of the sulfite ions, and if the content of the sulfite ions is smaller, the amount of the generated dark-color high molecular compound is small, so that the tinting effect of the product is reduced; if the content of sulfite ions is large, the oxidation reaction is excessive, and a blackish brown resin-like high-molecular compound is generated, resulting in high product viscosity, poor fluidity, and reduced quality. Furthermore, sulfite can form an addition compound with aldehydes, which inhibits the formation of ketoaldehyde reducing intermediates, so adding too much sulfite inhibits caramel browning.
Therefore, for the ammonium sulfite caramel color process, the effect of coloring the product cannot be achieved by only increasing sulfite, which is the root cause of poor coloring effect of the prepared caramel color caused by the existing ammonium sulfite caramel color process.
According to the invention, sulfamic acid, aluminum isopropoxide and ethylene glycol are added in the reaction, so that the coloring effect of the prepared caramel color can be obviously improved, and specifically:
in the Maillard reaction process, more amine substances can be generated, and a large amount of substances containing amide and sulfonic acid groups can be generated by adding sulfamic acid to react with the amine substances. And the amide and the sulfonic acid group are used as the color assisting group, so that the polarity of the caramel color is enhanced, and the coloring effect of the caramel color is greatly improved.
Aluminum isopropoxide is used as a strong dehydrating agent in a reaction system, and the dehydration condensation reaction in the Maillard reaction is further accelerated by adding the aluminum isopropoxide, so that the Maillard reaction is accelerated. Meanwhile, after the addition of aluminum isopropoxide, carbon-carbon double bonds (C ═ C) generated by enolization in the Maillard reaction process generate oxybenzone aroma to carbonyl compounds in the presence of ketone groups, and the double bonds are not influenced. The addition of carbon-carbon double bonds (C ═ C) in the caramel color can improve the red finger and oxidation resistance of the caramel color product, prevent the caramel color from being damaged by oxidation and improve the coloring stability and durability of the caramel color.
Carbonyl has various reaction properties and is one of more active energy-related groups, and carbonyl in caramel color is another important energy-related group for maintaining the oxidation resistance of the caramel color and improving the coloring stability and durability of the caramel color. Ethylene glycol, as a commonly used carbonyl protecting agent, can react with aldehydes and ketones to form cyclic acetals and ketals, which can protect carbonyl groups during the reaction. However, acetals and ketals are acid sensitive and weak acid solutions can effectively remove the protecting groups.
Therefore, in the reaction process, the ethylene glycol is added, the reaction materials are maintained in the alkaline state, the carbonyl group can be effectively protected, the acid is added after the reaction is stopped, the acid adjusting system is acidic, the protecting group is removed, and the oxidation resistance of the caramel color is improved, so that the coloring stability and the durability of the caramel color are improved.
Furthermore, the addition amount of the sulfamic acid is 0.05 to 0.10 percent of the syrup based on the dry base of the raw syrup.
Sulfamic acid, an inorganic solid acid formed by substituting the hydroxyl group of sulfuric acid with an amino group, and if the amount of the aqueous solution is too large, the aqueous solution has strong acidity equivalent to that of hydrochloric acid, sulfuric acid and the like, the reaction cannot be completed under alkaline conditions; the effect cannot be achieved when the dosage is too small, and multiple tests prove that 0.05-0.10% is the most suitable dosage.
Further, the adding amount of the aluminum isopropoxide is 0.02-0.08% of the syrup based on the dry base of the raw syrup.
Aluminum isopropoxide is used as a strong dehydrating agent, and after the syrup is added, the dehydrating effect of the syrup is intensified, so that the Maillard reaction is accelerated, if the adding amount is too large, the reaction is too fast, the production process is difficult to control, and the stability of the product is influenced. Tests prove that the dosage of 0.02 to 0.08 percent is most suitable for controlling and efficiency of the reaction process.
Furthermore, the addition amount of the glycol is 0.01-0.05% of the syrup based on the dry base of the raw syrup.
The excessive glycol has certain influence on the product quality, and tests prove that the coloring effect of the ammonium sulfite caramel color is best when the adding amount of 0.01-0.05% of the glycol is the best, and the product quality is not influenced when the metabolic oxidation amount of the glycol is the least.
Further, the pH value of the reaction system is controlled to be 7.0-7.5 in the reaction process.
Glycol reacts with aldehyde and ketone to generate cyclic acetal and cyclic ketal which are stable to reducing agent, oxidant under neutral or alkaline condition and various nucleophiles, thus protecting carbonyl in the reactions; however, if the syrup is too alkaline, the negative impact on the quality of the final caramel color (e.g., salt tolerance, viscosity) is great. Therefore, the alkalescence or neutrality is best in the reaction process.
Further, the pH value of the system is controlled to be 5.5-6.0 after the reaction is stopped.
Acetals and ketals are acid-sensitive, and very weak acid solutions can effectively remove protecting groups, so that the oxidation resistance of the caramel color is improved, and the coloring stability and durability of the caramel color are improved. However, if the pH value is too low, the pH value is slightly strong, and the adverse effects on the salt tolerance, viscosity, red index and the like of caramel color are large, so that the quality of caramel color is deteriorated.
Further, the method comprises the following steps:
s1, adding materials: adding sulfite, ammonia or ammonium compounds, sulfamic acid, aluminum isopropoxide and glycol into the raw material starch syrup;
s2, pH adjustment: controlling the reaction system to be alkaline in the reaction process, heating to react to a specified color ratio, and stopping the reaction;
s3, neutralization: cooling the material after the reaction is ended, and controlling the system to be acidic;
s4, filtering: the neutralized mass was filtered to obtain the desired caramel color solution.
Further, in step S2, during the reaction, the pH of the reaction system is controlled to be 7.0 to 7.5 by continuously adding liquid alkali.
The sulfite is one or more of sodium sulfite, sodium bisulfite, sodium pyrosulfite, sodium dithionate, potassium sulfite and potassium bisulfite.
The ammonia compound is ammonia or ammonia water or a mixture of the ammonia and the ammonia water.
The ammonium compound is one or more of ammonium sulfate, ammonium bisulfate, ammonium bisulfite, ammonium citrate, ammonium carbonate and ammonium bicarbonate.
The sulfite, ammonia or ammonium compounds are common raw materials for the ammonium sulfite method caramel color production process.
Further, in step S3, the neutralization is performed by controlling the pH of the system to 5.5-6.0 with an acid, and the acid used for the neutralization includes at least one of hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, and acetic acid.
The caramel color is prepared by the production process of the caramel color by the ammonium sulfite method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, sulfamic acid, aluminum isopropoxide and ethylene glycol are added in the existing ammonium sulfite-method caramel color reaction system, and the sulfamic acid generates a large amount of substances containing amide and sulfonic acid groups in the reaction system, so that the polarity of the caramel color is enhanced, and the coloring effect of the caramel color is greatly improved; the aluminum isopropoxide and the ethylene glycol can improve the coloring stability and durability of the caramel color; therefore, the caramel color coloring effect prepared by the ammonium sulfite method caramel color production process is obviously improved.
2. According to the method, sulfamic acid, aluminum isopropoxide and ethylene glycol are added into the existing reaction system for caramel color by the ammonium sulfite method, excessive sulfite is not needed, so that the phenomenon that sulfite and aldehyde form addition compounds which can inhibit the formation of ketone-aldehyde reducing intermediate products is avoided, and caramel browning can be inhibited by adding excessive sulfite.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Example 1:
this example illustrates the production of 36Be, 10000EBC caramel color (EBC is the color yield unit of caramel color; Be means the Baume value of caramel color, and both the color yield and Baume are the indexes for measuring caramel color):
an ammonium sulfite method caramel color production process comprises the following steps:
1) feeding: metering and feeding: metering malt syrup with the dry matter amount of 6000kg into a reaction tank;
2) adding a catalyst: adding 120kg of sodium sulfite, 30kg of ammonia, 3kg (0.05%) of sulfamic acid, 1.2kg (0.02%) of aluminum isopropoxide and 0.6kg (0.01%) of ethylene glycol;
3) adding alkali to adjust the pH value of the material to 7.0, heating for reaction, continuously adding alkali and monitoring the pH value of the reaction material to be 7.0-7.5, reacting until the color ratio is 0.058, and terminating the reaction;
4) cooling the reaction-terminated material, and adding citric acid to adjust the pH value of the material to 5.5;
5) and filtering: filtering the material after the reaction by a 200-mesh filter screen to remove impurities in the caramel color;
6) and blending: pumping the material into a blending tank, and blending according to the technical index requirements of color ratio, baume, acidity and the like;
7) metering and filling: and (4) metering, filling and warehousing and keeping the blended product.
Comparative example 1:
this comparative example is based on example 1 and differs from example 1 in that:
in the step 2), sulfamic acid, isopropanol and glycol are not added; the other steps and conditions were the same.
The caramel color prepared in example 1 and the caramel color prepared in comparative example 1 are compared with other sulfurous caramel colors for pork coloring, and the specific results are shown in Table 1:
TABLE 1
| Caramel color | Amount of the composition | Speed of coloring | Color strength | Durability |
| Comparative example 1 ammonium sulfite caramel color | 2g | -- | + | - |
| Example 1 ammonium sulfite caramel color | 2g | + | +++ | ++ |
Note: more "+" indicates better effect, more "-" indicates worse effect
Example 2:
this example is illustrated by the production of 36Be, 15000EBC caramel color (EBC is the color yield unit of caramel color; Be means the Baume value of caramel color, and both the color yield and Baume are the indexes for measuring caramel color):
an ammonium sulfite method caramel color production process comprises the following steps:
1) feeding: metering and feeding: the method comprises the following steps of (1) metering and adding 10000kg of malt syrup into a reaction tank;
2) and adding a catalyst: adding 180kg of sodium metabisulfite, 60kg of ammonium sulfate, 7.5kg (0.75%) of sulfamic acid, 5kg (0.05%) of aluminum isopropoxide and 3kg (0.03%) of ethylene glycol;
3) adding alkali to adjust the pH value of the material to 7.35, heating for reaction, continuously adding alkali and monitoring the pH value of the reaction material to be 7.0-7.5, reacting until the color ratio is 0.076, and stopping the reaction;
4) cooling the reaction-terminated material, and adding citric acid to adjust the pH value of the material to 5.8;
5) and filtering: filtering the material after the reaction by a 200-mesh filter screen to remove impurities in the caramel color;
6) and blending: pumping the material into a blending tank, and blending according to the technical index requirements of color ratio, baume, acidity and the like;
7) and metering and filling: and (4) metering, filling and warehousing and keeping the blended product.
Comparative example 2:
this comparative example is based on example 2, differing from example 2 in that:
in the step 2), sulfamic acid, isopropanol and glycol are not added; the other steps and conditions were the same.
The caramel color prepared in example 2 and the caramel color prepared in comparative example 2 are compared with other sulfurous caramel colors for pork coloring, and the specific results are shown in Table 2:
TABLE 2
Note: more "+" indicates better effect, more "-" indicates worse effect
Example 3:
this example is illustrated by the production of 36Be, 20000EBC caramel color (EBC is the color yield unit of caramel color; Be means the Baume value of caramel color, and both the color yield and Baume are the indexes for measuring caramel color):
an ammonium sulfite method caramel color production process comprises the following steps:
1) feeding: metering and feeding: adding the malt syrup with the dry matter amount of 15000kg into a reaction tank in a metering way;
2) and adding a catalyst: adding 240kg of sodium bisulfite, 90kg of ammonium carbonate, 15kg (0.10%) of sulfamic acid, 12kg (0.08%) of aluminum isopropoxide and 7.5kg (0.05%) of ethylene glycol;
3) adding alkali to adjust the pH value of the material to 7.5, heating for reaction, continuously adding alkali and monitoring the pH value of the reaction material to be 7.0-7.5, reacting until the color ratio is 0.095, and stopping the reaction;
4) cooling the material after the reaction is ended, and adding citric acid to adjust the pH value of the material to 6.0;
5) and filtering: filtering the material after the reaction by a 200-mesh filter screen to remove impurities in the caramel color;
6) and (3) blending: pumping the material into a blending tank, and blending according to the technical index requirements of color ratio, baume, acidity and the like;
7) and metering and filling: and (4) metering, filling and warehousing and keeping the blended product.
Comparative example 3:
this comparative example is based on example 3, differing from example 3 in that:
in the step 2), sulfamic acid, isopropanol and glycol are not added; the other steps and conditions were the same.
The caramel color prepared in example 3 and the caramel color prepared in comparative example 3 and other sulfurous acid method caramel colors are subjected to pork coloring comparison, and the specific results are shown in Table 3:
TABLE 3
| Caramel color | Dosage of | Coloring speed | Color strength | Durability |
| Comparative example 3 ammonium sulfite caramel color | 2g | + | ++ | --- |
| EXAMPLE 3 ammonium sulfite method caramel color | 2g | ++ | ++++ | ++ |
Note: the more "+" indicates better effect, the more "-" indicates worse effect
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A process for producing caramel color by an ammonium sulfite method is characterized in that sulfamic acid, aluminum isopropoxide and glycol are added into a reaction system of the ammonium sulfite method, the reaction system is controlled to be alkaline in the reaction process, and the reaction system is controlled to be acidic after the reaction is terminated.
2. The process of claim 1, wherein the amount of sulfamic acid added is 0.05 to 0.10 percent of the syrup on a dry basis of the starting syrup.
3. The process for producing caramel color by the ammonium sulfite method according to claim 1, wherein the amount of aluminum isopropoxide added is 0.02-0.08% of the syrup on a dry basis of the raw syrup.
4. The process of claim 1, wherein the amount of ethylene glycol added is 0.01-0.05% of the syrup on a dry basis.
5. The process for producing caramel color by the ammonium sulfite method according to claim 1, wherein the pH value of the reaction system is controlled to be 7.0-7.5 during the reaction.
6. The process for producing caramel color by the ammonium sulfite method according to claim 1, wherein the pH value of the system is controlled to be 5.5-6.0 after the reaction is terminated.
7. The ammonium sulfite caramel color production process according to claim 1, which comprises the following steps:
s1, adding materials: adding sulfite, ammonia or ammonium compounds, sulfamic acid, aluminum isopropoxide and glycol into the raw material starch syrup;
s2, pH adjustment: controlling the reaction system to be alkaline in the reaction process, heating to react to a specified color ratio, and stopping the reaction;
s3, neutralization: cooling the material after the reaction is ended, and controlling the system to be acidic;
s4, filtering: the neutralized mass was filtered to obtain the desired caramel color solution.
8. The process of claim 7, wherein in step S2, the pH of the reaction system is controlled to 7.0-7.5 by continuously adding liquid alkali.
9. The process of claim 7, wherein in step S3, the pH of the system is controlled to 5.5-6.0 by neutralization with an acid, and the acid used for neutralization comprises at least one of hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, and acetic acid.
10. Caramel color produced by the ammonium sulfite caramel color production process as claimed in any one of claims 1 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105062132A (en) * | 2015-09-10 | 2015-11-18 | 千禾味业食品股份有限公司 | Ammonium sulfite method-based caramel colour production process |
| CN105348852A (en) * | 2015-12-15 | 2016-02-24 | 千禾味业食品股份有限公司 | Process of ammonium sulfite method caramel color with color index being more than or equal to 250000EBC |
| WO2017216336A1 (en) * | 2016-06-16 | 2017-12-21 | Pfeifer & Langen GmbH & Co. KG | Stabilized burnt sugar |
| CN110003683A (en) * | 2019-04-24 | 2019-07-12 | 千禾味业食品股份有限公司 | A kind of preparation process of Sauce flavor burnt sugar coloring |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105062132A (en) * | 2015-09-10 | 2015-11-18 | 千禾味业食品股份有限公司 | Ammonium sulfite method-based caramel colour production process |
| CN105348852A (en) * | 2015-12-15 | 2016-02-24 | 千禾味业食品股份有限公司 | Process of ammonium sulfite method caramel color with color index being more than or equal to 250000EBC |
| WO2017216336A1 (en) * | 2016-06-16 | 2017-12-21 | Pfeifer & Langen GmbH & Co. KG | Stabilized burnt sugar |
| CN110003683A (en) * | 2019-04-24 | 2019-07-12 | 千禾味业食品股份有限公司 | A kind of preparation process of Sauce flavor burnt sugar coloring |
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