CN114772722A - Method for improving anaerobic digestion performance of hydrothermal wastewater by utilizing homologous hydrothermal carbon - Google Patents
Method for improving anaerobic digestion performance of hydrothermal wastewater by utilizing homologous hydrothermal carbon Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
Abstract
The invention belongs to the technical field of resource utilization of solid-liquid two-phase products of hydrothermal carbonization of biomass wastes, and particularly relates to a method for improving anaerobic digestion performance of hydrothermal wastewater by utilizing homologous hydrothermal carbon. By carrying out KOH modification treatment on hydrothermal carbon generated by hydrothermal carbonization of biomass waste and adding the hydrothermal carbon into an anaerobic digestion methane-producing reactor for homologous hydrothermal wastewater, the efficiency of the hydrothermal carbon for anaerobic digestion methane production is improved. The application method of the homologous hydrothermal carbon in the field of hydrothermal wastewater treatment obviously improves the conversion rate and the energy recovery rate of organic matters in the hydrothermal wastewater, avoids the use of exogenous biological carbon, is beneficial to reducing the anaerobic digestion treatment cost of the hydrothermal wastewater, and provides a new path for the resource utilization of solid-liquid products of a biomass hydrothermal carbonization process.
Description
Technical Field
The invention belongs to the technical field of resource utilization of hydrothermal carbonization solid-liquid two-phase products of biomass wastes, and particularly relates to a method for improving anaerobic digestion performance of hydrothermal wastewater by utilizing homologous hydrothermal carbon.
Background
Hydrothermal carbonization is an effective method for improving the quality of biomass fuel in a subcritical water environment, and the temperature and the pressure adopted are respectively 180 ℃ and 250 ℃ and 2-10 MPa. The biomass is subjected to hydrolysis, dehydration, decarboxylation, polymerization and aromatization reactions to generate hydrothermal carbon which is a solid product with high fuel quality, and simultaneously, a large amount of liquid by-products, namely hydrothermal wastewater, are generated. Anaerobic digestion is an economical and effective organic wastewater treatment technology. However, the hydrothermal wastewater has complex components and contains more biotoxic components (phenol, furan, pyrazine, pyridine, aldehyde, ketone, etc.) besides organic acids and carbohydrates which are easy to biodegrade, so that the anaerobic digestion process of the hydrothermal wastewater is unstable or the organic matter conversion efficiency is limited.
Therefore, it is necessary to take appropriate measures to reduce the biotoxicity inhibitory effect of the hydrothermal wastewater and to improve the organic matter conversion efficiency and methane yield.
Patent No. CN108384813B discloses a method for improving anaerobic digestion gas production performance of straw stalks by combined pretreatment of calcium oxide and biogas slurry. Although alkaline substance calcium oxide is used, the method only adopts the combination of calcium oxide and biogas slurry to pretreat the straw stalks so as to improve the yield of methane, does not carry out corresponding hydrothermal treatment on the straw stalks, and does not relate to the adverse effect of the biological toxic components of hydrothermal wastewater on the gas production performance of anaerobic digestion.
Patent No. CN113604510A discloses a method for improving efficiency of methane production by hydrothermal carbon enhanced anaerobic digestion, which includes performing ball milling modification treatment on hydrothermal carbon, increasing abundance of oxygen-containing functional groups exposed on the surface of hydrothermal carbon to improve its ability to mediate direct electron transfer in an anaerobic digestion system, and further improving efficiency of methane production by hydrothermal carbon enhanced anaerobic digestion, but does not perform alkaline treatment on hydrothermal carbon, and the patent is directed to anaerobic digestion performance of organic waste/wastewater (glucose water is used in the examples), and does not relate to adverse effect of biotoxic components of hydrothermal wastewater on anaerobic digestion gas production performance.
Various biomass pyrolytic carbons can improve the anaerobic digestion methanogenesis performance of organic wastewater by enriching anaerobic microorganisms and promoting direct electron transfer, but in order to treat hydrothermal wastewater by anaerobic digestion, the biomass pyrolytic carbons are usually required to be additionally prepared, and the preparation process of the biomass pyrolytic carbons needs higher temperature (over 500 ℃), so that the treatment cost of the hydrothermal wastewater is increased.
Disclosure of Invention
Based on the above disadvantages and shortcomings of the prior art, one of the objectives of the present invention is to solve at least one or more of the above problems of the prior art, in other words, to provide a method for hydrothermal modification of biomass and improving anaerobic digestion performance of hydrothermal wastewater by using homologous hydrothermal charcoal; the invention also aims to improve the operation stability of the anaerobic digestion system and the methane yield.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for improving the anaerobic digestion performance of hydrothermal wastewater by utilizing homologous hydrothermal carbon comprises the following steps:
(1) obtaining a slurry reaction product by using biomass waste through a hydrothermal carbonization mode, and separating to obtain hydrothermal carbon and hydrothermal wastewater;
(2) removing oily components adhered to the surface of the hot carbon;
(3) performing KOH modification on the hydrothermal carbon obtained in the step (2);
(4) and (4) adding the modified hydrothermal carbon obtained in the step (3) into an anaerobic digestion reactor for hydrothermal wastewater, adjusting the pH, and collecting a gas product.
Preferably, the biomass waste in the step (1) is any one of agricultural and forestry waste, sewage sludge and algae.
Preferably, the crushing size of the biomass waste is less than 1 mm, and the pore diameter of a fiber water system filter membrane for separating the hydrothermal solid-liquid product is between 0.3 and 0.5 mu m.
Preferably, the hydrothermal carbonization reaction temperature in the step (1) is 200-260 ℃, and the reaction time is 2-4 h.
Preferably, the solvent involved in the removal in the step (2) is an organic solvent.
Preferably, the organic solvent is tetrahydrofuran or ethanol.
Preferably, the hydrothermal carbon modification method in the step (2) is that the hydrothermal carbon and 2 mol/L KOH solution are mixed in a mass unit of gram to volume ratio unit of milliliter 1:50 and mixed well.
When the mixing ratio is too low, the surface characteristics of the hydrothermal carbon are not greatly changed, and when the mixing ratio is too high, a large amount of K can be loaded on the surface of the hydrothermal carbon+And is not easy to wash away.
As a preferable scheme, the adding amount of the modified hydrothermal carbon in the step (3) is 10-15 g/L.
The promoting effect is not significant below this range, and K in the modified hydrothermal carbon is not significant above this range+And heavy metals can generate toxicity to methanogens, the chemical oxygen demand of the hydrothermal wastewater is controlled to be 8-12 g/L, and when the concentration is too high, substrate overload can be caused, so that an anaerobic digestion system can be disabled or stopped.
Preferably, in the step (3), the anaerobic digestion temperature is 37 +/-2 ℃, and the hydrothermal wastewater and the inoculum are prepared into fermentation liquor according to the total chemical oxygen demand unit g of 1: 1.
Preferably, the initial pH of each anaerobic reactor in the step (3) is controlled to be 7.5 +/-0.1.
This pH is a value suitable for the survival of acid-producing bacteria and methanogenic bacteria.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention takes the homologous hydrothermal carbon generated by hydrothermal carbonization of biomass waste as an additive, and is applied to a system for generating methane by anaerobic digestion of hydrothermal wastewater which is a byproduct of hydrothermal carbonization, so that the hydrothermal carbon is utilized in a homologous manner, and the cost generated by additional preparation of the charcoal is reduced.
(2) The hydrothermal carbon is modified by KOH, the modified hydrothermal carbon has stronger promotion effect on the methane production performance of hydrothermal wastewater anaerobic digestion than the original hydrothermal carbon, so that the benefit of an anaerobic digestion process is higher, and the potassium hydroxide used as an alkaline modification reagent is beneficial to increasing the pore size and the abundance of oxygen-containing functional groups on the surface of the hydrothermal carbon, so that the conversion and utilization of organic components in the hydrothermal wastewater are more effectively realized.
(3) Reduces the toxic action of toxic components in the hydrothermal wastewater on methanogens.
(4) The conversion rate and the energy recovery rate of organic matters in the hydrothermal wastewater are obviously improved, the use of exogenous biochar is avoided, the anaerobic digestion treatment cost of the hydrothermal wastewater is favorably reduced, and a new path is provided for the resource utilization of solid-liquid products in a biomass hydrothermal carbonization process.
Drawings
FIG. 1 is a graph showing the cumulative methane production in each reactor in examples 1, 2 and 3 as a function of fermentation time
FIG. 2 is a flow chart of the preparation method of the present invention.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention, the following description will explain specific embodiments of the present invention with reference to the accompanying drawings. It is obvious that the drawings in the following description are only some examples of the invention, and that for a person skilled in the art, other drawings and embodiments can be derived from them without inventive effort.
The invention innovatively provides a method for improving anaerobic digestion performance of hydrothermal wastewater by utilizing homologous hydrothermal carbon produced by hydrothermal carbonization of biomass, the homologous hydrothermal carbon produced in the hydrothermal carbonization process is modified by KOH activation, the pore structure and the abundance of oxygen-containing functional groups on the surface of the hydrothermal carbon are improved, and the homologous hydrothermal carbon is added into a methane production reactor for anaerobic digestion of hydrothermal wastewater as a byproduct of hydrothermal carbonization, so that the direct electron transfer capability among microbial species mediated by the hydrothermal carbon is obviously improved, the toxic action of toxic components in the hydrothermal wastewater on methane bacteria is reduced, and the lag phase of the methane production process by anaerobic digestion is shortened. Increase the resource utilization gradient of hydrothermal charcoal on the one hand, on the other hand avoids extra preparation of exogenous biomass pyrolytic carbon, compares in exogenous biomass pyrolytic carbon, and the abundant oxygen-containing functional group in hydrothermal charcoal surface can also adsorb control waste water toxicity component and be favorable to improving electron transfer efficiency, and this patent further improves the pore structure and the surface oxygen-containing functional group abundance of hydrothermal charcoal promptly through KOH modification, is showing the anaerobic digestion operating stability who improves hydrothermal waste water and improves methane output.
In the following examples, an inoculum is required for anaerobic reaction, the inoculum is taken from a corn stalk anaerobic fermentation substrate of a certain enterprise in the city of the state of the province of the Hebei province, the inoculum is acclimatized in a constant-temperature water bath at 37 +/-0.2 ℃ for two weeks before an anaerobic digestion experiment is started so as to improve the activity of microorganisms and reduce the gas production of the inoculum, and then the hydrothermal wastewater and the inoculum are prepared into fermentation liquor according to the total chemical oxygen demand of 1: 1.
Example 1:
s1 the corn straw is ground and crushed by a high-speed grinder and is sieved by a sieve of 1 mm to obtain straw powder with the particle size of less than 18 meshes.
S2 adding 100g of corn stalk powder and 600g of deionized water into a pressurized stirred tank reactor with a working volume of 1L, obtaining a reaction product under the conditions of 250 ℃ and 2h, and filtering with a 0.45 mu m fiber filter membrane to obtain hydrothermal carbon and hydrothermal wastewater.
S3 the oily components and degradable organic matters on the surface of the hydrothermal charcoal are repeatedly washed with deionized water and tetrahydrofuran until the washed liquid becomes clear, and then the hydrothermal charcoal is dried and ground through a 0.3mm sieve.
S4, mixing the dried hydrothermal carbon with 2 mol/L KOH solution, wherein the mass unit of the dried hydrothermal carbon is gram, and the volume unit of the dried hydrothermal carbon is milliliter, and the weight ratio of the dried hydrothermal carbon to the volume unit of the KOH solution is 1:50 (w: v), placing in an oscillating water bath with the temperature of 30 ℃ and the rotating speed of 150 rpm for oscillating for 2h, centrifuging the immersed suspension in a centrifuge at the rotating speed of 9500 rpm for 10 min to obtain the modified hydrothermal carbon, drying and grinding the modified hydrothermal carbon by a 0.3mm sieve.
S5 three sets of anaerobic reactors were set up, with each set of experiments in triplicate. Anaerobic digestion was carried out in a 500 mL fermentor flask with a working volume of 300 mL. The chemical oxygen demand of the hydrothermal wastewater is controlled to be 10 g/L, the total chemical oxygen demand of the organic wastewater and the total chemical oxygen demand of the inoculum are inoculated according to the ratio of 1:1, and the three groups of reactors are respectively added with no water-heated carbon, 15 g/L of original water-heated carbon and 15 g/L of modified water-heated carbon. The initial pH of each reactor was adjusted to 7.5. + -. 0.1, and then the prepared reactor was purged with nitrogen for 5min to create an anaerobic environment, and anaerobic digestion was carried out in a constant temperature shaking water bath at 37. + -. 2 ℃.
S6 gas production is obtained by liquid displacement method, the daily gas production is collected by an aluminum foil gas collection bag, the sampling interval is 24h, and the gas chromatograph equipped with a thermal conductivity detector is used for measuring the component content of the gas production, the carrier gas is argon gas, the flow rate is 20 mL/min, the temperature of a column box is 80 ℃, the temperature of a sample inlet is 120 ℃, the temperature of a flame ionization detector is 200 ℃, the flow rate of a column is 8 mL/min, and the split ratio is 5. The flow chart of the preparation method and the cumulative methane yield of each reactor are shown in figure 1.
As can be seen from FIG. 1, the effect of the modified hydrothermal carbon on the methane production of the hydrothermal wastewater by anaerobic digestion is obviously better than that of the original hydrothermal carbon.
Example 2:
s1, the dried sludge is ground and crushed by a high-speed grinder and is sieved by an 18-mesh sieve to obtain powder with the particle size of less than 1 mm.
S2 adding 100g of sludge powder and 600g of deionized water into a pressurized stirred tank reactor with a working volume of 1L, obtaining a reaction product under the conditions of 250 ℃ and 2h, and filtering by a fiber filter membrane with the diameter of 0.45 mu m to obtain hydrothermal carbon and hydrothermal wastewater.
S3 the oily components and degradable organic matters on the surface of the hydrothermal charcoal are repeatedly washed with deionized water and tetrahydrofuran until the washed liquid becomes clear, and then the hydrothermal charcoal is dried and ground through a 0.3mm sieve.
S4, mixing the dried hydrothermal carbon with 2 mol/L KOH solution in terms of mass unit of grams and volume unit of milliliters in terms of 1:50 (w: v), placing the mixture in an oscillating water bath with the temperature of 30 ℃ and the rotating speed of 150 rpm for oscillation for 2 hours, centrifuging the immersed suspension in a centrifuge at the rotating speed of 9500 rpm for 10 minutes to obtain the modified hydrothermal carbon, drying and grinding the modified hydrothermal carbon through a 0.3mm sieve.
S5 three sets of anaerobic reactors were set up, with each set of experiments performed in triplicate. Anaerobic digestion was carried out in a 500 mL fermentor flask with a working volume of 300 mL. The chemical oxygen demand of the hydrothermal wastewater is controlled to be 10 g/L, the total chemical oxygen demand of the organic wastewater and the total chemical oxygen demand of the inoculum are inoculated according to the ratio of 1:1, and the three groups of reactors are respectively added with 10 g/L original hydrothermal carbon and 10 g/L modified hydrothermal carbon without adding hydrothermal carbon. The initial pH of each reactor was adjusted to 7.5. + -. 0.1, and then the prepared reactor was purged with nitrogen for 5min to create an anaerobic environment, and anaerobic digestion was carried out in a constant temperature shaking water bath at 37. + -. 2 ℃.
S6 gas production is obtained by liquid displacement method, the daily gas production is collected by an aluminum foil gas collection bag, the sampling interval is 24h, and the gas chromatograph equipped with a thermal conductivity detector is used for measuring the component content of the gas production, the carrier gas is argon gas, the flow rate is 20 mL/min, the temperature of a column box is 80 ℃, the temperature of a sample inlet is 120 ℃, the temperature of a flame ionization detector is 200 ℃, the flow rate of a column is 8 mL/min, and the split ratio is 5. The cumulative methane production for each reactor is shown in figure 1.
As can be seen from FIG. 1, the effect of the modified hydrothermal carbon on the methane production of the hydrothermal wastewater by anaerobic digestion is obviously better than that of the original hydrothermal carbon.
Example 3:
s1, the dried poplar branches are ground and crushed by a high-speed grinder and pass through an 18-mesh sieve to obtain powder with the particle size of less than 1 mm.
S2 adding 100g poplar branch powder and 600g deionized water into a pressurized stirred tank reactor with a working volume of 1L, obtaining a reaction product under the conditions of 250 ℃ and 2h, and filtering with a 0.45 mu m fiber filter membrane to obtain hydrothermal carbon and hydrothermal wastewater.
S3 the oily components and degradable organic matters on the surface of the hydrothermal charcoal are repeatedly washed with deionized water and tetrahydrofuran until the washed liquid becomes clear, and then the hydrothermal charcoal is dried and ground through a 0.3mm sieve.
S4, mixing the dried hydrothermal carbon with 2 mol/L KOH solution in terms of mass unit of grams and volume unit of milliliters in terms of 1:50 (w: v), placing the mixture in an oscillating water bath with the temperature of 30 ℃ and the rotating speed of 150 rpm for oscillation for 2 hours, centrifuging the immersed suspension in a centrifuge at the rotating speed of 9500 rpm for 10 minutes to obtain the modified hydrothermal carbon, drying and grinding the modified hydrothermal carbon through a 0.3mm sieve.
S5 three sets of anaerobic reactors were set up, with each set of experiments in triplicate. Anaerobic digestion was carried out in a 500 mL fermentor flask with a working volume of 300 mL. The chemical oxygen demand of the hydrothermal wastewater is controlled to be 10 g/L, the total chemical oxygen demand of the organic wastewater and the total chemical oxygen demand of the inoculum are inoculated according to the ratio of 1:1, and the three groups of reactors are respectively added with 12.5 g/L original hydrothermal carbon and 12.5 g/L modified hydrothermal carbon without adding hydrothermal carbon. The initial pH of each reactor was adjusted to 7.5 + -0.1, and then the configured reactor was purged with nitrogen for 5min to create an anaerobic environment, the anaerobic digestion was carried out in a constant temperature oscillating water bath at 37 + -2 deg.C.
S6 gas production is obtained by liquid displacement method, the daily gas production is collected by an aluminum foil gas collection bag, the sampling interval is 24h, and the gas chromatograph equipped with a thermal conductivity detector is used for measuring the component content of the gas production, the carrier gas is argon gas, the flow rate is 20 mL/min, the temperature of a column box is 80 ℃, the temperature of a sample inlet is 120 ℃, the temperature of a flame ionization detector is 200 ℃, the flow rate of a column is 8 mL/min, and the split ratio is 5. The cumulative methane production for each reactor is shown in figure 1.
As can be seen from FIG. 1, the effect of the modified hydrothermal carbon on the methane production of the hydrothermal wastewater by anaerobic digestion is obviously better than that of the original hydrothermal carbon.
By carrying out KOH modification treatment on hydrothermal carbon generated by hydrothermal carbonization of biomass waste and adding the hydrothermal carbon into an anaerobic digestion methane-producing reactor for homologous hydrothermal wastewater, the strengthening efficiency of the hydrothermal carbon on the anaerobic digestion methane-producing performance is improved. The cumulative methane yield of the experimental group added with the corn straw, the sludge and the poplar wood chip modified hydrothermal carbon is respectively increased by 30.7%, 24.2% and 25.7% compared with that of the experimental group added with the original hydrothermal carbon, and is increased by 42.7%, 47.7% and 37.4% compared with that of the experimental group added with no hydrothermal carbon, as shown in Table 1.
TABLE 1
According to the invention, biomass waste is subjected to hydrothermal carbonization to prepare hydrothermal carbon, and a hydrothermal wastewater byproduct is generated; the hydrothermal carbon is subjected to KOH modification and is added into an anaerobic digestion methane production reactor for hydrothermal wastewater, so that the yield of accumulated methane generated by anaerobic digestion of the hydrothermal wastewater is remarkably improved, and the running stability of an anaerobic digestion system is enhanced. The application method of the homologous hydrothermal carbon in the field of hydrothermal wastewater treatment provided by the invention obviously improves the conversion rate and the energy recovery rate of organic matters in the hydrothermal wastewater, avoids the use of exogenous biological carbon, is beneficial to reducing the anaerobic digestion treatment cost of the hydrothermal wastewater, and provides a new path for the resource utilization of solid-liquid products in a biomass hydrothermal carbonization process.
The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention so that those skilled in the art may better understand the detailed description of the invention that follows.
Claims (10)
1. A method for improving the anaerobic digestion performance of hydrothermal wastewater by utilizing homologous hydrothermal carbon is characterized by comprising the following steps:
obtaining a slurry reaction product by using biomass waste through a hydrothermal carbonization mode, and separating to obtain hydrothermal carbon and hydrothermal wastewater;
removing oily components adhered to the surface of the hot carbon;
(3) performing KOH modification on the hydrothermal carbon obtained in the step (2);
(4) and (4) adding the modified hydrothermal carbon obtained in the step (3) into an anaerobic digestion reactor for hydrothermal wastewater, adjusting the pH, and collecting a gas product.
2. The method for improving the anaerobic digestion performance of hydrothermal wastewater by using homologous hydrothermal charcoal according to claim 1, wherein the biomass waste in step (1) is any one of agricultural and forestry waste, sewage sludge and algae.
3. The method for improving the anaerobic digestion performance of hydrothermal wastewater by using the homologous hydrothermal charcoal according to claim 1, wherein the biomass waste in the step (1) is pulverized to have a size of less than 1 mm.
4. The method for improving the anaerobic digestion performance of hydrothermal wastewater by using homologous hydrothermal carbon as claimed in claim 1, wherein the hydrothermal carbonization reaction temperature in step (1) is 200-260 ℃ and the reaction time is 2-4 h.
5. The method for improving the anaerobic digestion performance of hydrothermal wastewater by using homologous hydrothermal charcoal according to claim 1, wherein the solvent used for removing the oily components on the surface of the hydrothermal charcoal in step (2) is an organic solvent.
6. The method for improving the anaerobic digestion performance of hydrothermal wastewater by using homologous hydrothermal charcoal according to claim 5, wherein the organic solvent is tetrahydrofuran or ethanol.
7. The method for improving the anaerobic digestion performance of hydrothermal wastewater by using homologous hydrothermal charcoal according to claim 1, wherein the hydrothermal charcoal modification method in step (3) is to mix the hydrothermal charcoal with 2 mol/L KOH solution in gram by mass and milliliter by volume to obtain 1:50 and mixing well.
8. The method for improving the anaerobic digestion performance of hydrothermal wastewater by using homologous hydrothermal charcoal according to claim 1, wherein the dosage of the modified hydrothermal charcoal in the step (4) is 10-15 g/L, and the chemical oxygen demand of the hydrothermal wastewater is controlled to be 8-12 g/L.
9. The method for improving the anaerobic digestion performance of the hydrothermal wastewater by using the homologous hydrothermal carbon according to claim 1, wherein the anaerobic digestion temperature in the step (4) is 37 ± 2 ℃, and the hydrothermal wastewater and the inoculum are prepared into a fermentation broth with the total Chemical Oxygen Demand (COD) unit g being 1: 1.
10. The method for improving the anaerobic digestion performance of hydrothermal wastewater by using homologous hydrothermal charcoal according to claim 1, wherein the initial pH of each anaerobic reactor in the step (4) is controlled to 7.5 ± 0.1.
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