CN114716843B - Production process of caramel color by ammonium sulfite method and caramel color - Google Patents
Production process of caramel color by ammonium sulfite method and caramel color Download PDFInfo
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- CN114716843B CN114716843B CN202210545367.6A CN202210545367A CN114716843B CN 114716843 B CN114716843 B CN 114716843B CN 202210545367 A CN202210545367 A CN 202210545367A CN 114716843 B CN114716843 B CN 114716843B
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- 239000000940 FEMA 2235 Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 56
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 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 22
- 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 21
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 235000020357 syrup Nutrition 0.000 claims description 20
- 239000006188 syrup Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 16
- 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 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 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
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000006386 neutralization reaction 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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 21
- 230000000694 effects Effects 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 5
- 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
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 7
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 235000013736 caramel Nutrition 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
- -1 ammonia compound Chemical class 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
- 239000000243 solution Substances 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
- 239000003054 catalyst Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005259 measurement Methods 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
- 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
- 241000544912 Melanoides Species 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
- 150000001241 acetals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000015784 hyperosmotic salinity response Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 235000020429 malt syrup Nutrition 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920000642 polymer Polymers 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
- 229940001584 sodium metabisulfite Drugs 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
- 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 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
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products 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 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
- 125000003277 amino group Chemical group 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
- 239000007864 aqueous solution Substances 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
- 150000002085 enols Chemical class 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
- 229940011411 erythrosine Drugs 0.000 description 1
- 239000004174 erythrosine Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 239000011973 solid acid 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 caramel color production process and caramel color, wherein sulfamic acid, aluminum isopropoxide and ethylene glycol are added into an ammonium sulfite 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 stopped; specifically, the pH value of the reaction system is controlled to be 7.0-7.5 in the reaction process; the pH value of the system is controlled to be 5.5-6.0 after the reaction is stopped. According to the invention, sulfamic acid, aluminum isopropoxide and ethylene glycol are added into the existing reaction system of caramel color by an ammonium sulfite method, and sulfamic acid generates a large amount of substances containing amide and sulfonic acid groups in the reaction system, so that the polarity of 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 prepared by the ammonium sulfite method caramel color production process has obviously improved coloring effect.
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 a caramel color.
Background
The caramel color has wide use tradition in China, is the edible pigment with the largest dosage, and has extremely important function in the food field. Caramel color can be divided into four main categories according to the different production processes: ordinary process caramel color, caustic sulfite process caramel color, ammonia process caramel color, ammonium sulfite process caramel color. The caramel color is prepared by taking carbohydrate as a main raw material and adding or not adding acid (alkali) under the existence of ammonia compound and sulfite.
Caramel color by ammonium sulfite method caramel is negatively charged, has good acid resistance and salt resistance, has relatively strong coloring capability, and is widely applied in the food industry. GB 2760-2014 "national food safety Standard food additive usage Standard" specifies: the caramel color obtained by the ammonium sulfite method can be used in the production and processing of condensed milk, various beverages, cocoa products, chocolate products, candies, batter, instant grains, biscuits, soy sauce and sauce products. In China, the caramel color by an ammonium sulfite method is one of main ingredients of soy sauce and sauce products. The caramel color by the ammonium sulfite method has wide application range and high cost performance, is favored by wide food factories, and has the sales volume accounting for more than 60 percent of the total caramel color product.
But relative to other pigments such as natural pigment red yeast red, sorghum red, radish red; compared with synthetic pigments such as erythrosine, sunset yellow, lemon yellow, carmine and the like, the caramel color prepared by the ammonium sulfite method has weak tinting strength, slow tinting, relatively narrow tinting scope and relatively poor tinting stability. The invention aims to obviously improve the coloring intensity, speed, applicable range and stability of the caramel color by the ammonium sulfite method through a process technology for improving the coloring power of the caramel color by the ammonium sulfite method so as to adapt to 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 the prepared caramel color caused by the existing production technology of caramel color by the ammonium sulfite method.
In addition, the invention also provides the caramel color prepared by the ammonium sulfite caramel color production process.
The invention is realized by the following technical scheme:
The caramel color production process with ammonium sulfite method includes adding sulfamic acid, aluminum isopropoxide and glycol into the reaction system with ammonium sulfite method, controlling the reaction system to be alkaline during the reaction, and controlling the reaction system to be acidic after the reaction is terminated.
The existing reaction system of the caramel color production process by the ammonium sulfite method is that sulfite, ammonia or ammonium compounds are added into raw material syrup to carry out Maillard reaction.
The syrup and free amino in ammonia or ammonium compound undergo a series of reactions including condensation, dehydrogenation, rearrangement, isomerization and the like to finally form a brown polymer or copolymer containing nitrogen, which is called melanoid, wherein the melanoid is a complex high molecular mixture with unknown molecular structure, and the mixture contains unsaturated bonds, heterocyclic structures and some residues.
In the reaction process, the product of the Maillard reaction can interact with sulfite ions to generate oxidation reaction to generate dark high molecular compounds, 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 dark high molecular compounds is small, so that the tinting effect of the product is reduced; if the content of sulfite ions is large, oxidation reaction becomes excessive, and a blackish brown resin-like polymer compound is produced, resulting in high product viscosity, poor fluidity, and reduced quality. In addition, sulphite can form addition compounds with aldehydes which inhibit the formation of ketoaldehyde reducing intermediates, so the addition of too much sulphite inhibits caramel browning.
Therefore, for the caramel color process of the ammonium sulfite method, the coloring effect of the product is not realized only by adding sulfite, which is the root cause of poor coloring effect of the prepared caramel color caused by the existing caramel color process of the ammonium sulfite method.
According to the invention, sulfamic acid, aluminum isopropoxide and ethylene glycol are added simultaneously 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 are generated, and sulfamic acid is added to react with the amine substances to generate a large amount of substances containing amide and sulfonic acid groups. And the amide and the sulfonic acid groups are used as auxiliary color groups, so that the polarity of caramel color is enhanced, and the coloring effect of the caramel color is greatly improved.
The aluminum isopropoxide is used as a strong dehydrating agent in a reaction system, and the addition of the aluminum isopropoxide can further aggravate the dehydration condensation reaction in the Maillard reaction, thereby accelerating the Maillard reaction. Meanwhile, after aluminum isopropoxide is added into a carbon-carbon double bond (C=C) generated by enolization in the Maillard reaction process, under the participation of ketone groups, the enol is subjected to the oxidation of the obronol to carbonyl compounds, and the double bond is not affected. The addition of the carbon-carbon double bond (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 reactivity, is one of more active functional groups, and carbonyl in caramel color is another important functional group for maintaining oxidation resistance of the caramel color and improving coloring stability and durability of the caramel color. Ethylene glycol, which is a commonly used carbonyl protectant, can form cyclic acetals with aldehydes and ketones, and cyclic ketals can protect carbonyl groups during the reaction. However, acetals and ketals are acid sensitive and weak acid solutions are effective in removing protecting groups.
Therefore, in the reaction process, glycol is added, the reaction materials are maintained at alkaline energy to effectively protect carbonyl groups, and after the reaction is stopped, the acid addition regulating system is acidic to remove the protecting group, so that the oxidation resistance of the caramel color is improved, and the coloring stability and durability of the caramel color are improved.
Further, the sulfamic acid is added in an amount of 0.05 to 0.10 percent of the syrup based on the dry basis of the raw material syrup.
Sulfamic acid is an inorganic solid acid formed by substituting hydroxyl groups of sulfuric acid with amino groups, and if the dosage of the sulfamic acid 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 dosage is too small to achieve the effect, and experiments prove that 0.05 to 0.10 percent is the most suitable dosage.
Further, the addition amount of the aluminum isopropoxide is 0.02-0.08% of the syrup based on the dry basis of the raw material syrup.
When aluminum isopropoxide is used as a strong dehydrating agent, the dehydrating effect of the syrup can be enhanced after the aluminum isopropoxide is added into the syrup, so that the Maillard reaction becomes fast, and 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 can be influenced. Experiments prove that the dosage of 0.02% -0.08% is most suitable for controlling the reaction process and the efficiency.
Further, the addition amount of the glycol is 0.01% -0.05% of the syrup based on the dry basis of the raw material syrup.
The excessive ethylene glycol has a certain influence on the quality of the product, and experiments prove that the addition amount of 0.01% -0.05% of ethylene glycol has the best coloring effect on the caramel color by an ammonium sulfite method, and the metabolic oxidation amount of the ethylene glycol is the least, namely, the quality of the product is not influenced.
Further, the pH value of the reaction system is controlled to be 7.0-7.5 in the reaction process.
Ethylene glycol reacts with aldehydes and ketones to form cyclic acetals and ketals which are stable to reducing agents, oxidizing agents under neutral or alkaline conditions and various nucleophiles, thus protecting carbonyl groups in these reactions; however, if the syrup is too alkaline, the final caramel color quality (e.g., salt tolerance, viscosity) is greatly negatively affected. Therefore, weakly basic or neutral is preferred during the reaction.
Further, the pH value of the system is controlled to be 5.5-6.0 after the reaction is stopped.
The acetal and ketal are sensitive to acid, and the weak acid solution can effectively remove the protecting group, thereby improving the oxidation resistance of the caramel color and further improving the coloring stability and durability of the caramel color. However, if the pH value is too low, the pH value is slightly more acidic, and the adverse effects on salt tolerance, viscosity, red index and the like of caramel color are larger, and the caramel color quality is deteriorated.
Further, the method comprises the following steps:
S1, adding materials: adding sulfite, ammonia or ammonium compounds, sulfamic acid, aluminum isopropoxide and ethylene glycol into raw material starch syrup;
s2, pH adjustment: controlling the reaction system to be alkaline in the reaction process, heating to react to a designated color rate, and terminating the reaction;
S3, neutralization: cooling the material which is stopped to react, 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, the pH value of the reaction system is controlled to be 7.0-7.5 by adopting a continuous flow liquid alkali adding mode in the reaction process.
The sulfite is one or more of sodium sulfite, sodium bisulfite, sodium metabisulfite, sodium dithionite, potassium sulfite and potassium hydrogen sulfite.
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 citrate, ammonium carbonate and ammonium bicarbonate.
The sulfite, ammonia or ammonium compounds are all common raw materials for the caramel color production process of the ammonium sulfite method.
Further, in the step S3, the pH value of the system is controlled to be 5.5-6.0 by using acid in the neutralization, and the acid used in the neutralization at least comprises one of hydrochloric acid, sulfuric acid, phosphoric acid, citric acid and acetic acid.
The caramel color prepared by the caramel color production process by the ammonium sulfite method is as described above.
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 into the existing reaction system of caramel color by an ammonium sulfite method, and sulfamic acid generates a large amount of substances containing amide and sulfonic acid groups in the reaction system, so that the polarity of 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 prepared by the ammonium sulfite method caramel color production process has obviously improved coloring effect.
2. According to the invention, sulfamic acid, aluminum isopropoxide and ethylene glycol are added into the existing reaction system for the caramel color by an ammonium sulfite method, so that excessive sulfite is not needed to be used, the sulfite can be prevented from forming an addition compound with aldehyde, the compound can inhibit the formation of ketoaldehyde reducing intermediate products, and excessive sulfite can inhibit caramel browning.
Detailed Description
The present invention will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, and the description thereof is merely illustrative of the present invention and not intended to be limiting.
Example 1:
This example describes the production of 36Be,10000EBC caramel color (EBC is the color ratio unit of caramel color; be refers to the Baume value of caramel color, and both the color ratio and Baume are measurement indexes of caramel color):
a production process of caramel color by an ammonium sulfite method comprises the following steps:
1) Feeding: metering and feeding: metering a dry malt syrup in an amount of 6000kg into a reaction tank;
2) And (3) adding a catalyst: 120kg of sodium sulfite, 30kg of ammonia, 3kg of sulfamic acid (0.05%), 1.2kg of aluminum isopropoxide (0.02%), 0.6kg of ethylene glycol (0.01%) are added;
3) Adding alkali to adjust the pH value of the material to 7.0, heating the material for reaction, continuously adding alkali, monitoring the pH value of the reaction material to be maintained at 7.0-7.5, reacting until the color ratio is 0.058, and stopping the reaction;
4) Cooling the material which is stopped to react, and adding citric acid to adjust the pH value of the material to 5.5;
5) And (3) filtering: filtering the reacted material through a 200-mesh filter screen to remove impurities in the caramel color;
6) And (3) blending: pumping the materials into a blending tank, and blending according to the technical index requirements of color ratio, baume, acidity and the like;
7) And (5) metering and filling: and (5) metering and filling the blended product, and warehousing and keeping.
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 ethylene glycol are not added; other steps and conditions were the same.
Caramel color prepared in example 1 and comparative example 1 other sulfurous acid process caramel colors were compared for pork color, and the specific results are shown in table 1:
TABLE 1
| Caramel color | Dosage of | Speed of coloring | Color strength | Durability of |
| Comparative example 1 caramel color by the ammonium sulfite method | 2g | -- | + | - |
| Example 1 caramel color by the ammonium sulfite method | 2g | + | +++ | ++ |
Note that: more "+" indicates better effect, and more "-" indicates worse effect
Example 2:
this example describes the production of 36Be,15000EBC caramel color (EBC is the color ratio unit of caramel color; be refers to the Baume value of caramel color, and both the color ratio and Baume are measurement indexes of caramel color):
a production process of caramel color by an ammonium sulfite method comprises the following steps:
1) Feeding: metering and feeding: metering maltose syrup with a dry matter amount of 10000kg into a reaction tank;
2) And (3) adding a catalyst: 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 are added;
3) Adding alkali to adjust the pH value of the materials to 7.35, heating the materials for reaction, continuously adding alkali, monitoring the pH value of the reaction materials to be maintained at 7.0-7.5, reacting until the color ratio is 0.076, and stopping the reaction;
4) Cooling the material which is stopped to react, and adding citric acid to adjust the pH value of the material to 5.8;
5) And (3) filtering: filtering the reacted material through a 200-mesh filter screen to remove impurities in the caramel color;
6) And (3) blending: pumping the materials into a blending tank, and blending according to the technical index requirements of color ratio, baume, acidity and the like;
7) And (5) metering and filling: and (5) metering and filling the blended product, and warehousing and keeping.
Comparative example 2:
this comparative example is based on example 2, and differs from example 2 in that:
in the step 2), sulfamic acid, isopropanol and ethylene glycol are not added; other steps and conditions were the same.
Caramel color prepared in example 2 and comparative example 2 other sulfurous acid process caramel colors were compared for pork color, and the specific results are shown in table 2:
TABLE 2
Note that: more "+" indicates better effect, and more "-" indicates worse effect
Example 3:
this example describes the production of 36Be,20000EBC caramel color (EBC is the color index unit of caramel color; be refers to the Baume value of caramel color, and both the color index and Baume are measurement indexes of caramel color):
a production process of caramel color by an ammonium sulfite method comprises the following steps:
1) Feeding: metering and feeding: malt syrup in an amount of 15000kg of dry matter was metered into the reaction tank;
2) And (3) adding a catalyst: 240kg of sodium bisulphite, 90kg of ammonium carbonate, 15kg of sulfamic acid (0.10%), 12kg of aluminum isopropoxide (0.08%), 7.5kg of ethylene glycol (0.05%) are added;
3) Adding alkali to adjust the pH value of the materials to 7.5, heating the materials for reaction, continuously adding alkali, monitoring the pH value of the reaction materials to be maintained at 7.0-7.5, reacting until the color ratio is 0.095, and stopping the reaction;
4) Cooling the material which is stopped to react, and adding citric acid to adjust the pH value of the material to 6.0;
5) And (3) filtering: filtering the reacted material through a 200-mesh filter screen to remove impurities in the caramel color;
6) And (3) blending: pumping the materials into a blending tank, and blending according to the technical index requirements of color ratio, baume, acidity and the like;
7) And (5) metering and filling: and (5) metering and filling the blended product, and warehousing and keeping.
Comparative example 3:
this comparative example is based on example 3, and differs from example 3 in that:
in the step 2), sulfamic acid, isopropanol and ethylene glycol are not added; other steps and conditions were the same.
Caramel color prepared in example 3 and comparative example 3 other sulfurous acid process caramel colors were compared for pork color, and the specific results are shown in table 3:
TABLE 3 Table 3
| Caramel color | Dosage of | Speed of coloring | Color strength | Durability of |
| Comparative example 3 caramel color by the ammonium sulfite method | 2g | + | ++ | --- |
| EXAMPLE 3 caramel color by the ammonium sulfite method | 2g | ++ | ++++ | ++ |
Note that: more "+" indicates better effect, and more "-" indicates worse effect
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The production process of caramel color by ammonium sulfite method is characterized by adding sulfamic acid, aluminum isopropoxide and ethylene glycol into a reaction system by ammonium sulfite method, and controlling the reaction system to be alkaline in the reaction process, wherein the alkaline refers to pH value of 7.0-7.5, and the reaction system is controlled to be acidic after termination of the reaction.
2. The process for producing caramel color by an ammonium sulfite method as claimed in claim 1, wherein the sulfamic acid is added in an amount of 0.05 to 0.10 percent of the syrup based on the dry basis of the raw material syrup.
3. The process for producing caramel color by an ammonium sulfite method as claimed in claim 1, wherein the addition amount of the aluminum isopropoxide is 0.02 to 0.08 percent of the syrup based on the dry basis of the raw material syrup.
4. The process for producing caramel color by an ammonium sulfite method as claimed in claim 1, wherein the addition amount of the glycol is 0.01% -0.05% of the syrup based on the dry basis of the raw material syrup.
5. The process for producing caramel color by the ammonium sulfite method as claimed in claim 1, wherein the pH value of the system is controlled to be 5.5-6.0 after the reaction is stopped.
6. The process for producing caramel color by an ammonium sulfite method as claimed in claim 1, comprising the following steps:
S1, adding materials: adding sulfite, ammonia or ammonium compounds, sulfamic acid, aluminum isopropoxide and ethylene glycol into raw material starch syrup;
S2, pH adjustment: controlling the reaction system to be alkaline in the reaction process, heating to react to a designated color rate, and terminating the reaction; controlling the reaction system to be alkaline in the reaction process means controlling the pH value of the reaction system to be 7.0-7.5 by adopting a continuous flow liquid alkali adding mode;
S3, neutralization: cooling the material which is stopped to react, and controlling the system to be acidic;
s4, filtering: the neutralized mass was filtered to obtain the desired caramel color solution.
7. The process according to claim 6, wherein in step S3, the pH of the system is controlled to be 5.5-6.0 by using an acid, and the acid used for neutralization at least comprises one of hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, and acetic acid.
8. Caramel color produced by the ammonium sulfite caramel color production process of any one of claims 1-7.
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| 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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| 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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