CN106957736B - A kind of non-phosphate detergent of strong detergency and preparation method thereof - Google Patents

Abstract

The present invention provides non-phosphate detergents of a kind of strong detergency and preparation method thereof, and specifically the non-phosphate detergent of strong detergency provided by the invention includes washing protease, enzyme stabilizers and surfactant；Wherein, the washing is 10000u/ml-500000u/ml with protease content, and enzyme stabilizers content is 3%-15% (w/v), and surface-active contents are 1%-15% (v/v).The non-phosphate detergent of strong detergency of the invention is free of boracic stabilizer, and enzyme activity stabilization can significantly extend the detergent shelf-life.

Description

A kind of non-phosphate detergent of strong detergency and preparation method thereof

Technical field

The invention belongs to environmental science and technology fields, specifically, the present invention relates to a kind of non-phosphate detergent of strong detergency and Preparation method.

Background technique

Detergent is the daily necessities of people's life and the necessity of industrial production etc..The production of China's detergent Amount has reached annual 3000000 tons, and with the speed increase of annual 3.4%.The type of detergent is more as washing powder, tableware are clear Lotion, toilet detergent, carpet detergent, metal detergent, greasy dirt detergent etc..Detergent by surfactant, help Lotion, filler and small powder (such as brightening agent, essence) composition, builder is mainly phosphate i.e. sodium tripolyphosphate.According to washing The different function of agent is washed, phosphate is also different in content wherein, generally between 20~40%.Some developed countries In high phosphorus detergent, sodium tripolyphosphate can account for 50~60% content.In recent ten years, with the quick hair of China's economy Exhibition, the output of sodium tripolyphosphate also increase considerably.Output is at annual 50~600,000 tons at present.

There are about the washes containing 50~600,000 tons of sodium tripolyphosphates to discharge every year in China, and these phosphorus-containing wastewaters are mostly Rivers,lakes and seas are flowed into.Accounted for about according to the difference of area surroundings and be discharged into the 20~60% of total phosphorus content and differ, has substantially exceeded water body The ability of auto-degradation nitrogen, phosphorus.Nitrogen, phosphorus, potassium in water are more than the eutrophication that certain content is water quality, will lead to algae because Nutrient is excessively sufficient and mushrooms out breeding.A part of raised growth breeding, another part mortality become limpid dark green water quality Muddy it must can't bear, there have been algal tufa phenomenons.Dead algae is in kermesinus across the sea in ocean, therefore referred to as red tide. Marine environment expert for many years to water quality monitoring summary conclude that in normal seawater, in water N/P ratio should be 16: 1 with It is interior, when reaching this ratio and nitrogen, phosphorus concentration increase, along with extraneous some reasons.Such as temperature increases, all kinds of algaes It begins to breed rapidly, red tide phenomenon gradually occurs.

In conclusion the phosphate in phosphorus-containing detergent is very serious to rivers,lakes and seas pollution, it is forbidden to use phosphorus-containing detergent, Just become the optimal path for solving phosphorus pollution.Therefore those skilled in the art be dedicated to developing the production technology of new detergent, Formula produces non-phosphate detergent.

Detergent using enzyme as auxiliary agent is referred to as enzyme detergent, and compared with conventional washing agent, enzyme detergent is gone Dirty ability is stronger, and application range is wider.Phosphorus-containing detergent can be thus replaced to meet the daily and industrial requirement of people.It is washed adding It washs in agent, enzyme is usually unstable, and polar solvent, buffer and its various cationic and anionic surfactant components may change enzyme The higher structure of albumen.The unstability of enzyme annoyings always the exploitation and production of entire enzyme liquid detergent industry, liquid Detergent puts forward new requirements the stability of enzyme.

Summary of the invention

The purpose of the present invention is to provide non-phosphate detergents of a kind of strong detergency and preparation method thereof.

Under study for action inventors have surprisingly discovered that used experiment protease enzyme activity under the conditions of long-term place shows It is more stable.On this basis, the present inventor further studies, it is found that certain small peptides can press down as the invertibity of protease Preparation plays stablizing effect to protease.It therefore, can be with the present invention provides a kind of enzyme stabilizers safely, effectively, nontoxic The genotoxicity problem for avoiding common boracic stabilizer, improves liquid basified protease storage stability.

The characteristics of present invention is formulated according to Fermented Condensed enzyme designs enzyme stabilizers, can be substantially reduced production and processing and storage The precipitating and extension liquid basified protease shelf life of middle formation.

The first aspect of the present invention, provides a kind of non-phosphate detergent of strong detergency, including washing protease, enzyme are steady Determine agent and surfactant；Wherein, the washing is 10000u/ml-500000u/ml with protease content, and enzyme stabilizers contain Amount is 3%-15% (w/v), and surface-active contents are 1%-15% (v/v).

Preferably, the detergent is liquid concentration detergent.

Preferably, the washing is alkali protease with protease.

Preferably, the surfactant is that heterogeneous ten alcohol polyoxyethylene ether, ethoxylated dodecyl alcohol or alkyl phenol are poly- Ethylene oxide ether.

Preferably, the enzyme stabilizers include: calcium lactate, 1,2 propylene glycol and small peptide additive, the small peptide additive For QRY, KNY or QNW.

It preferably, include: calcium lactate 0.5-10 parts by weight, 1,2 propylene glycol 2-10 parts by weight, small peptide in the enzyme stabilizers Additive 0.05-0.5 parts by weight.

It is highly preferred that including: that calcium lactate 1-3 parts by weight, 1,2 propylene glycol 3-8 parts by weight, small peptide add in the enzyme stabilizers Add agent 0.1-0.3 parts by weight.

In another preferred example, the enzyme activity of the liquid enzyme additives is preferably 100000u/ml-300000u/ml.

In another preferred example, the alkali protease is bacillus licheniformis (Bacillus licheniformis) production Raw alkali protease.

In another preferred example, the content of the surfactant is preferably 5%-10% (v/v).

In another preferred example, the pH of the detergent is 4-7, preferably 4.5-6.5.

" alkali protease " in the present invention refers to, is suitable for a kind of protease used under the alkaline condition of pH9-11 Preparation can be made from bacillus subtilis or bacillus licheniformis, Pichia yeast fermentation, product is available commercially Savinase, Alcalase, alkali protease2709 (the bacillus licheniformis hair obtained such as Novi's letter fermentation of bacillus subtilis Ferment is made) etc..

The liquid enzyme detergent of concentration of the invention is preferably the concentrated product of liquid detergent to be added.Due to liquid Enzyme amount used in enzyme additive is bigger, easily generates precipitating, and enzyme activity is very unstable.It is preferably carried out in mode, is concentrated Liquid enzyme detergent in enzyme amount be at least 10000u/ml, and be no more than 500000u/ml.

It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist This no longer tires out one by one states.

Specific embodiment

Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to manufactory Condition proposed by quotient.Unless otherwise stated, otherwise percentage and number are calculated by weight.

The preparation of 1 enzyme stabilizers of embodiment

1. the design and screening of small peptide additive

To reach the alkali protease storage activity for improving liquid, the condition of product is improved, we have developed one kind can Improve the alkaline protease inhibitor of Stability of Liquid Alkaline Protease.

It is devised tens of according to the restriction enzyme site of alkali protease with reference to the stereochemical structure information of alkali protease first Small peptide, representative small peptide is as shown in table 1, and wherein amino acid residue is indicated by one-letter abbreviations, and designed small peptide is transferred to The synthesis of gill biochemistry (Shanghai) Co., Ltd..

2. preparing liquid concentration detergent and detecting preservation effect

Enzyme stabilizers are prepared, include: calcium lactate 2g, 1 in enzyme stabilizers, 2 propylene glycol 6g and small peptide additive 0.2g are mixed It closes uniform.It takes 100ml alkali protease enzyme solution (alkali protease2709,200000U/ml), the enzyme of above-mentioned preparation is added in stirring Then 5% (v/v) heterogeneous ten alcohol polyoxyethylene ether (CAS:61827-42-7) is added in stabilizer.

Adjusting the above each group liquid concentration detergent pH is 5.5, does not add remaining component one of small peptide additive in control group It causes, after 40 DEG C save 1 month, detects enzyme activity storage rate.

Enzyme activity assay method, the reagent used and instrument refer to national standard GBT23527-2009

Bacillus licheniformis source alkali protease2709 (CAS:9014-01-1), which contains (Shanghai) biotechnology purchased from the summer, to be had Limit company.The Enzyme assay commission summer contains (Shanghai) Biotechnology Co., Ltd's application technical research development centre and carries out and provide Examining report, detection method are as follows:

1 enzyme activity calculates

X=A × K × 8/2 × 1/10 × n × E=2/5 × A × K × n × E

In formula:

X: the enzyme activity (u/g or u/ml) of sample；

A: the mean light absorbency of sample solution；

K: extinction constant；

8: the total volume (ml) of reaction reagent；

2: enzyme solution 2.00ml is drawn, in terms of ml；

1/10: reaction time 10min, in terms of min；

N: extension rate；

E: (neutral, alkaline coefficient is 0.50 to the conversion coefficient of ultraviolet method and folin's methods, 0.77) acid protease coefficient is Acquired results are indicated to integer.

2 enzyme activity storage rates

X=E₁/ E × 100%

X: the enzyme activity storage rate % of sample

E₁: sample surveys enzyme activity (u/g or u/ml)

E: sample marker (before preservation) enzyme activity (u/g or u/ml)

Experimental result is as shown in table 1.From table 1 it follows that No. 2 small peptides, No. 4 small peptides, No. 5 small peptides, No. 6 small peptides, No. 7 Small peptide shows preferable enzyme activity preservation effect.

Table 1

Small peptide number	Short peptide sequence	Enzyme activity storage rate %	Condition variation
				1	FPR	13.2%	It is slightly muddy
2	KNP	64.4%	It is slightly muddy
				3	QGF	32.6%	Clarification
4	QNW	90.5%	Clarification
				5	KNY	87.1%	Clarification
6	KRW	74.5%	Clarification
				7	QRY	92.6%	Clarification
Control	Nothing	12.7%	It is muddy

Table 1 the result shows that, No. 2 small peptides, No. 4 small peptides, No. 5 small peptides, No. 6 small peptides, the effect of No. 7 small peptides are preferable.Then We have further investigated influence of the pH to enzyme activity stability, adjust different pH, detect different short peptide sequences in each pH item The enzyme activity stability shown under part, each three groups of experimental group setting parallel, and detection method is same as above.

Table 2

The result combination table 1 of table 2, it can be seen that for small peptide 2 when pH is 6.5, enzyme activity preservation effect is best；Small peptide 6 is in pH When being 6.5, enzyme activity preservation effect is best；And small peptide 4,5,7 pH be 5.5 when, enzyme activity preservation effect is best.

All references mentioned in the present invention is incorporated herein by reference, independent just as each document It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims It encloses.

Claims (8)

1. a kind of non-phosphate detergent of strong detergency, which is characterized in that living including washing protease, enzyme stabilizers and surface Property agent；Wherein, the washing is 10000u/ml-500000u/ml with protease content, and enzyme stabilizers content is 3%-15% W/v, surface-active contents are 1%-15% v/v；The washing is alkali protease with protease；

The enzyme stabilizers include: calcium lactate, 1,2- propylene glycol and small peptide additive, the small peptide additive be QRY, KNY, Or QNW.

2. non-phosphate detergent as described in claim 1, which is characterized in that the non-phosphate detergent is liquid concentration detergent.

3. non-phosphate detergent as described in claim 1, which is characterized in that the small peptide additive is QRY.

4. non-phosphate detergent as described in claim 1, which is characterized in that the small peptide additive is KNY.

5. non-phosphate detergent as claimed in claim 4, which is characterized in that include: calcium lactate 0.5-10 in the enzyme stabilizers Parts by weight, 1,2- propylene glycol 2-10 parts by weight, small peptide additive 0.05-0.5 parts by weight.

6. non-phosphate detergent as described in claim 1, which is characterized in that include: calcium lactate 1-3 weight in the enzyme stabilizers Part, 1,2- propylene glycol 3-8 parts by weight, small peptide additive 0.1-0.3 parts by weight.

7. non-phosphate detergent as described in claim 1, which is characterized in that the content of the surfactant is 5%-10% v/v。

8. non-phosphate detergent as described in claim 1, which is characterized in that the pH of the detergent is 4-7.